EP3230261B1 - Naphthyl acrylate as write monomers for photopolymers - Google Patents
Naphthyl acrylate as write monomers for photopolymers Download PDFInfo
- Publication number
- EP3230261B1 EP3230261B1 EP15807900.4A EP15807900A EP3230261B1 EP 3230261 B1 EP3230261 B1 EP 3230261B1 EP 15807900 A EP15807900 A EP 15807900A EP 3230261 B1 EP3230261 B1 EP 3230261B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- moiety
- formula
- binaphthyl
- group
- diyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- -1 Naphthyl acrylate Chemical compound 0.000 title claims description 154
- 239000000178 monomer Substances 0.000 title claims description 28
- 239000000203 mixture Substances 0.000 claims description 92
- 150000001875 compounds Chemical class 0.000 claims description 59
- 238000009472 formulation Methods 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 150000002367 halogens Chemical group 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229920000768 polyamine Polymers 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 229940124530 sulfonamide Drugs 0.000 claims description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- VUUAEBBAUMJPRE-UHFFFAOYSA-N ethyl n-fluorocarbamate Chemical compound CCOC(=O)NF VUUAEBBAUMJPRE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims 6
- 150000003857 carboxamides Chemical group 0.000 claims 4
- 239000005864 Sulphur Substances 0.000 claims 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 219
- 239000012948 isocyanate Substances 0.000 description 44
- 150000002513 isocyanates Chemical class 0.000 description 43
- 239000000975 dye Substances 0.000 description 40
- 239000007787 solid Substances 0.000 description 38
- 150000003254 radicals Chemical class 0.000 description 33
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 20
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 17
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 17
- 239000005056 polyisocyanate Substances 0.000 description 16
- 229920001228 polyisocyanate Polymers 0.000 description 16
- FZQMJOOSLXFQSU-UHFFFAOYSA-N 3-[3,5-bis[3-(dimethylamino)propyl]-1,3,5-triazinan-1-yl]-n,n-dimethylpropan-1-amine Chemical compound CN(C)CCCN1CN(CCCN(C)C)CN(CCCN(C)C)C1 FZQMJOOSLXFQSU-UHFFFAOYSA-N 0.000 description 15
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- 229920005862 polyol Polymers 0.000 description 15
- 150000003077 polyols Chemical class 0.000 description 15
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 101000801643 Homo sapiens Retinal-specific phospholipid-transporting ATPase ABCA4 Proteins 0.000 description 8
- 102100033617 Retinal-specific phospholipid-transporting ATPase ABCA4 Human genes 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- 239000004417 polycarbonate Substances 0.000 description 8
- 229920000515 polycarbonate Polymers 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 150000001450 anions Chemical class 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000012230 colorless oil Substances 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229920005906 polyester polyol Polymers 0.000 description 6
- 150000005846 sugar alcohols Polymers 0.000 description 6
- OORIFUHRGQKYEV-UHFFFAOYSA-N 6-bromo-1-(6-bromo-2-hydroxynaphthalen-1-yl)naphthalen-2-ol Chemical compound BrC1=CC=C2C(C3=C4C=CC(Br)=CC4=CC=C3O)=C(O)C=CC2=C1 OORIFUHRGQKYEV-UHFFFAOYSA-N 0.000 description 5
- WKTNIBWKHNIPQR-UHFFFAOYSA-N 6-hydroxynaphthalene-2-carbonitrile Chemical compound C1=C(C#N)C=CC2=CC(O)=CC=C21 WKTNIBWKHNIPQR-UHFFFAOYSA-N 0.000 description 5
- 125000005521 carbonamide group Chemical group 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 5
- ZWVMLYRJXORSEP-LURJTMIESA-N (2s)-hexane-1,2,6-triol Chemical compound OCCCC[C@H](O)CO ZWVMLYRJXORSEP-LURJTMIESA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 4
- WJIOHMVWGVGWJW-UHFFFAOYSA-N 3-methyl-n-[4-[(3-methylpyrazole-1-carbonyl)amino]butyl]pyrazole-1-carboxamide Chemical compound N1=C(C)C=CN1C(=O)NCCCCNC(=O)N1N=C(C)C=C1 WJIOHMVWGVGWJW-UHFFFAOYSA-N 0.000 description 4
- YLDFTMJPQJXGSS-UHFFFAOYSA-N 6-bromo-2-naphthol Chemical compound C1=C(Br)C=CC2=CC(O)=CC=C21 YLDFTMJPQJXGSS-UHFFFAOYSA-N 0.000 description 4
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical group N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000001001 arylmethane dye Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 3
- OBIGPOGFLBZPFB-UHFFFAOYSA-N 1-isocyanato-2-phenylsulfanylbenzene Chemical compound O=C=NC1=CC=CC=C1SC1=CC=CC=C1 OBIGPOGFLBZPFB-UHFFFAOYSA-N 0.000 description 3
- BKJABLMNBSVKCV-UHFFFAOYSA-N 1-isocyanato-3-methylsulfanylbenzene Chemical compound CSC1=CC=CC(N=C=O)=C1 BKJABLMNBSVKCV-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 3
- AYCWOJDHYWCEHK-UHFFFAOYSA-N 6-bromo-1-(2-hydroxynaphthalen-1-yl)naphthalen-2-ol Chemical compound BrC1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 AYCWOJDHYWCEHK-UHFFFAOYSA-N 0.000 description 3
- OJAXFLWDKVHHML-UHFFFAOYSA-N 6-hydroxy-5-(2-hydroxynaphthalen-1-yl)naphthalene-2-carbonitrile Chemical compound OC1=C(C2=CC=CC=C2C=C1)C1=C(O)C=CC2=CC(=CC=C12)C#N OJAXFLWDKVHHML-UHFFFAOYSA-N 0.000 description 3
- UNFNRIIETORURP-UHFFFAOYSA-N 7-methoxynaphthalen-2-ol Chemical compound C1=CC(O)=CC2=CC(OC)=CC=C21 UNFNRIIETORURP-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- DZUMXWOJZIAAGI-UHFFFAOYSA-N [1-(2-hydroxynaphthalen-1-yl)naphthalen-2-yl] N-[6-[[1-(2-hydroxynaphthalen-1-yl)naphthalen-2-yl]oxycarbonylamino]hexyl]carbamate Chemical compound C(CCCCCNC(OC1=C(C2=CC=CC=C2C=C1)C1=C(C=CC2=CC=CC=C12)O)=O)NC(OC1=C(C2=CC=CC=C2C=C1)C1=C(C=CC2=CC=CC=C12)O)=O DZUMXWOJZIAAGI-UHFFFAOYSA-N 0.000 description 3
- RNHPDPYMMDCMPJ-UHFFFAOYSA-N [2-[1-(2-carbamoyloxynaphthalen-1-yl)naphthalen-2-yl]oxycarbonylimino-2-prop-2-enoyloxyethyl] prop-2-enoate Chemical compound C(C=C)(=O)OCC(=NC(=O)OC1=C(C2=CC=CC=C2C=C1)C1=C(C=CC2=CC=CC=C12)OC(N)=O)OC(C=C)=O RNHPDPYMMDCMPJ-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000001414 amino alcohols Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 3
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 3
- KGLSETWPYVUTQX-UHFFFAOYSA-N tris(4-isocyanatophenoxy)-sulfanylidene-$l^{5}-phosphane Chemical compound C1=CC(N=C=O)=CC=C1OP(=S)(OC=1C=CC(=CC=1)N=C=O)OC1=CC=C(N=C=O)C=C1 KGLSETWPYVUTQX-UHFFFAOYSA-N 0.000 description 3
- 150000003673 urethanes Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 2
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 2
- VOGLMWWQIMVCDO-UHFFFAOYSA-N 1-(2-hydroxy-7-methoxynaphthalen-1-yl)-7-methoxynaphthalen-2-ol Chemical compound C1=C(OC)C=C2C(C3=C(O)C=CC4=CC=C(C=C43)OC)=C(O)C=CC2=C1 VOGLMWWQIMVCDO-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 description 2
- GPYLCFQEKPUWLD-UHFFFAOYSA-N 1h-benzo[cd]indol-2-one Chemical compound C1=CC(C(=O)N2)=C3C2=CC=CC3=C1 GPYLCFQEKPUWLD-UHFFFAOYSA-N 0.000 description 2
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 2
- DPNXHTDWGGVXID-UHFFFAOYSA-N 2-isocyanatoethyl prop-2-enoate Chemical compound C=CC(=O)OCCN=C=O DPNXHTDWGGVXID-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- JYXHVNGMYSCWDJ-UHFFFAOYSA-N 4-[1-(2-carbamoyloxynaphthalen-1-yl)naphthalen-2-yl]oxycarbonylimino-2,7-dimethylocta-2,6-dienedioic acid Chemical compound CC(C(O)=O)=CCC(C=C(C)C(O)=O)=NC(OC(C=CC1=CC=CC=C11)=C1C(C1=CC=CC=C1C=C1)=C1OC(N)=O)=O JYXHVNGMYSCWDJ-UHFFFAOYSA-N 0.000 description 2
- NQSYNHMPCXIHPZ-UHFFFAOYSA-N 5-(6-bromo-2-hydroxynaphthalen-1-yl)-6-hydroxynaphthalene-2-carbonitrile Chemical compound OC1=C(C2=CC=C(Br)C=C2C=C1)C1=C(O)C=CC2=CC(=CC=C12)C#N NQSYNHMPCXIHPZ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
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- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Images
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/30—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/48—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
- C07C323/43—Y being a hetero atom
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/38—Esters containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/52—Amides or imides
- C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
- G03C1/733—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds with macromolecular compounds as photosensitive substances, e.g. photochromic
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H2001/0208—Individual components other than the hologram
- G03H2001/022—Writing means other than actinic light wave
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
- G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
- G03H2001/026—Recording materials or recording processes
- G03H2001/0264—Organic recording material
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
- G03H2260/00—Recording materials or recording processes
- G03H2260/12—Photopolymer
Definitions
- the invention relates to naphthyl acrylates, which can be used in particular as writing monomers in photopolymer formulations for holographic media.
- a photopolymer formulation comprising matrix polymers, random monomers and photoinitiators, the random monomers comprising a naphthyl acrylate of the invention, a holographic medium comprising matrix polymers, random monomers and photoinitiators, the random monomers comprising a naphthyl acrylate of the invention and a display comprising a holographic medium of the invention Objects of the invention.
- Photopolymer formulations are known in the art.
- EP 2 154 128 describes a photopolymer formulation containing polyurethane-based matrix polymers, acrylate-based random monomers, and photoinitiators.
- the writing monomers and the photoinitiators are spatially distributed isotropically in the polyurethane matrix.
- document P2013014533 describes similar compounds for use in polymerization.
- 2011054818 describes similar compounds for use in photopolymerization.
- the refractive index modulation ⁇ n produced by the holographic exposure in the photopolymer plays the crucial role.
- the interference field of signal and reference light beam (in the simplest case that of two plane waves) is imaged by the local photopolymerization of, for example, high-index acrylates in high-intensity locations in the interference field in a refractive index grating.
- the refractive index grating in the photopolymer contains all the information of the signal light beam.
- the DE results from the quotient of the intensity of the light diffracted during the reconstruction and the sum of the intensities of the radiated reference light and the diffracted light.
- High refractive index acrylates are capable of producing high amplitude refractive index gratings between low refractive index regions and high refractive index regions, thereby allowing high DE and high ⁇ n holograms in photopolymers.
- the DE depends on the product of ⁇ n and the photopolymer layer thickness d depends. The larger the product, the larger the potential DE (for reflection holograms).
- the width of the spectral range which may contribute to the reconstruction of the hologram, likewise depends only on the layer thickness d. In this case, the smaller the d the greater the acceptance widths. If you want to produce therefore bright and easily visible holograms, a high ⁇ n and a small thickness d is desirable and in such a way that the DE is as large as possible. That is, the higher ⁇ n becomes, the more freedom to design the layer thickness d for bright holograms is achieved without loss of DE. Therefore, the optimization of ⁇ n in the optimization of photopolymer formulations is of paramount importance ( P. Hariharan, Optical Holography, 2nd Edition, Cambridge University Press, 1996 ).
- the compound of formula (I) is very suitable as a writing monomer for the production of holographic media with a very high refractive index contrast ( ⁇ n) and high optical quality.
- the compounds of the formula (I) according to the invention can be prepared, for example, in the following manner:
- symmetrical or non-symmetrical bis-naphthols can be prepared and optionally separated by preparative means, which then in a subsequent synthesis step with OH-reactive compounds to acrylates can be implemented.
- the compound according to the invention is substituted at the carbon atom of position 5 in the formula (I) with the radical of formula (III), wherein the radical of formula (III) preferably via the carbon atom of the position 8 'may be bonded to the carbon atom of position 5.
- radical of formula (III) is substituted on the carbon atom of position 7 'by the radical R ' of the formula (IV).
- Arcyl X stands for carbonamide and / or in the radical R, Arcyl ' X stands for carbonamide.
- radical R Arcyl R 1 is hydrogen or a CH 3 radical and / or in the radical R Arcyl ' R 1 ' is hydrogen or a CH 3 radical.
- Arcyl Y may be a -CH 2 -CH 2 radical and / or in which the radical R may be a -CH 2 -CH 2 radical.
- the compound of the formula (I) according to the invention is selected from the group of the following substances: 2 - [( ⁇ [2 '- ( ⁇ [2- (acryloyloxy) ethyl] carbamoyl ⁇ oxy) -1,1'-binaphthyl- 2-yl] oxy ⁇ carbonyl) amino] ethyl methacrylate, dimethyl 2,2'-bis ( ⁇ [2- (methacryloyloxy) ethyl] carbamoyl ⁇ oxy) -1,1'-binaphthyl-3,3'-dicarboxylate, diethyl 2,2'-bis ( ⁇ [2- (methacryloyloxy) ethyl] carbamoyl ⁇ oxy) -1,1'-binaphthyl-3,3'-dicarboxylate, 1,1'-binaphthyl-2,2'-diylbis (oxycarbonyliminoethane -2,1-
- a further subject of the invention is a photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, the writing monomers comprising a compound of the formula (I) according to the invention.
- the matrix polymers of the photopolymer formulation according to the invention can in particular be crosslinked and particularly preferably crosslinked three-dimensionally.
- the matrix polymers are polyurethanes, where the polyurethanes can be obtained in particular by reacting at least one polyisocyanate component a) with at least one isocyanate-reactive component b).
- the polyisocyanate component a) preferably comprises at least one organic compound having at least two NCO groups. These organic compounds may in particular be monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers.
- the polyisocyanate component a) may also contain or consist of mixtures of monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers.
- monomeric di- and triisocyanates it is possible to use all the compounds or mixtures thereof which are well known to the person skilled in the art. These compounds may have aromatic, araliphatic, aliphatic or cycloaliphatic structures. In subordinate In amounts, the monomeric di- and triisocyanates may also comprise monoisocyanates, ie organic compounds having an NCO group.
- Suitable monomeric di- and triisocyanates are 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 2,2,4-trimethylhexamethylene diisocyanate and / or 2,4,4-trimethylhexamethylene diisocyanate ( TMDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, bis (4,4'-isocyanatocyclohexyl) methane and / or bis (2 ', 4-isocyanatocyclohexyl) methane and / or their mixtures any desired isomer content, 1,4-cyclohexane diisocyanate, the isomeric bis (isocyanatomethyl) cyclohexanes, 2,4- and / or 2,6-diisocyan
- Suitable polyisocyanates are compounds having urethane, urea, carbodiimide, acylurea, amide, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and / or iminooxadiazinedione structures which are obtainable from the abovementioned di- or triisocyanates.
- the polyisocyanates are particularly preferably oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates, it being possible in particular to use the abovementioned aliphatic and / or cycloaliphatic di- or triisocyanates.
- Suitable prepolymers contain urethane and / or urea groups and optionally further structures formed by modification of NCO groups as mentioned above.
- Such prepolymers are obtainable, for example, by reacting the abovementioned monomeric di- and triisocyanates and / or polyisocyanates a1) with isocyanate-reactive compounds b1).
- isocyanate-reactive compounds b1) it is possible to use alcohols, amino or mercapto compounds, preferably alcohols. These may in particular be polyols. With very particular preference as isocyanate-reactive compound b1) Polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols can be used.
- Suitable polyester polyols are, for example, linear polyester diols or branched polyester polyols which can be obtained in a known manner by reacting aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality ⁇ 2.
- suitable di- or polycarboxylic acids are polybasic carboxylic acids such as succinic, adipic, cork, sebacic, decanedicarboxylic, phthalic, terephthalic, isophthalic, tetrahydrophthalic or trimellitic acid, as well as acid anhydrides such as phthalic, trimellitic or succinic anhydride or their arbitrary mixtures among themselves.
- the polyester polyols can also be based on natural raw materials such as castor oil. It is likewise possible for the polyesterpolyols to be based on homopolymers or copolymers of lactones, which preferably by addition of lactones or lactone mixtures such as butyrolactone, ⁇ -caprolactone and / or methyl- ⁇ -caprolactone to hydroxy-functional compounds such as polyhydric alcohols of an OH functionality ⁇ 2, for example, of the type mentioned below can be obtained.
- suitable alcohols are all polyhydric alcohols such as the C 2 - C 12 diols, the isomeric cyclohexanediols, glycerol or any mixtures thereof.
- Suitable polycarbonate polyols are obtainable in a manner known per se by reacting organic carbonates or phosgene with diols or diol mixtures.
- Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.
- Suitable diols or mixtures include the polyhydric alcohols of an OH functionality ⁇ 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpentanediol, which are per se in the context of the polyester segments. Polyester polyols can also be converted to polycarbonate polyols.
- Suitable polyether polyols are optionally block-formed polyaddition of cyclic ethers to OH or NH-functional starter molecules.
- Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin and any desired mixtures thereof.
- the starter used may be the polyhydric alcohols having an OH functionality ⁇ 2 and primary or secondary amines and amino alcohols, which are known per se within the scope of the polyester polyols.
- Preferred polyether polyols are those of the aforementioned type based solely on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides. Particular preference is given to propylene oxide homopolymers and also random or block copolymers which contain oxyethylene, oxypropylene and / or oxybutylene units, the proportion of oxypropylene units, based on the total amount of all oxyethylene, oxypropylene and oxybutylene units, being at least 20% by weight at least 45% by weight.
- Oxypropylene and oxybutylene here include all respective linear and branched C 3 and C 4 isomers.
- polystyrene resin as polyfunctional, isocyanate-reactive compounds and low molecular weight, i. with molecular weights ⁇ 500 g / mol, short chain, i. 2 to 20 carbon atoms containing aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols suitable.
- neopentyl glycol 2-ethyl-2-butylpropanediol, trimethylpentanediol, positional isomeric diethyloctanediols, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1,4- Cyclohexanediol, hydrogenated bisphenol A, 2,2-bis (4-hydroxy-cyclohexyl) -propane or 2,2-dimethyl-3-hydroxypropionic acid, 2,2-dimethyl-3-hydroxypropyl ester.
- triols examples are trimethylolethane, trimethylolpropane or glycerol.
- Suitable higher-functionality alcohols are di (trimethylolpropane), pentaerythritol, dipentaerythritol or sorbitol.
- the polyol component is a difunctional polyether, polyester or a polyether-polyester block copolyester or a polyether-polyester block copolymer having primary OH functions.
- amines as isocyanate-reactive compounds b1).
- suitable amines are ethylenediamine, propylenediamine, diaminocyclohexane, 4,4'-dicyclohexylmethanediamine, isophoronediamine (IPDA), difunctional polyamines, e.g. the Jeffamine®, amine-terminated polymers, in particular having number average molecular weights ⁇ 10000 g / mol. Mixtures of the aforementioned amines can also be used.
- amino alcohols as isocyanate-reactive compounds b1).
- suitable amino alcohols are the isomeric aminoethanols, the isomeric aminopropanols the isomeric aminobutanols and the isomeric aminohexanols or any mixtures thereof.
- All of the aforementioned isocyanate-reactive compounds b1) can be mixed with one another as desired.
- the isocyanate-reactive compounds b1) have a number-average molecular weight of ⁇ 200 and ⁇ 10000 g / mol, more preferably ⁇ 500 and ⁇ 8000 g / mol and very particularly preferably ⁇ 800 and ⁇ 5000 g / mol.
- the OH functionality of the polyols is preferably 1.5 to 6.0, particularly preferably 1.8 to 4.0.
- the prepolymers of the polyisocyanate component a) may in particular have a residual content of free monomeric diisocyanates and triisocyanates ⁇ 1% by weight, particularly preferably ⁇ 0.5% by weight and very particularly preferably ⁇ 0.3% by weight.
- the polyisocyanate component a) may comprise completely or proportionally organic compound whose NCO groups have been completely or partially reacted with blocking agents known from coating technology.
- blocking agents are alcohols, lactams, oximes, malonic esters, pyrazoles and amines, such as e.g. Butanone oxime, diisopropylamine, diethyl malonate, acetoacetic ester, 3,5-dimethylpyrazole, ⁇ -caprolactam, or mixtures thereof.
- the polyisocyanate component a) comprises compounds having aliphatically bonded NCO groups, aliphatic NCO groups being understood to mean those groups which are bonded to a primary carbon atom.
- the isocyanate-reactive component b) preferably comprises at least one organic compound which has on average at least 1.5 and preferably from 2 to 3 isocyanate-reactive groups. In the context of the present invention, hydroxy, amino or mercapto groups are preferably considered as isocyanate-reactive groups.
- the isocyanate-reactive component may in particular comprise compounds which have a number average of at least 1.5 and preferably 2 to 3 isocyanate-reactive groups.
- Suitable polyfunctional, isocyanate-reactive compounds of component b) are, for example, the compounds b1) described above.
- the writing monomers comprise a mono- and / or a multifunctional (meth) acrylate writing monomer.
- the random monomers may additionally comprise at least one mono- and / or one multifunctional urethane (meth) acrylate.
- Suitable acrylate writing monomers are, in particular, compounds of the general formula (II) in which n ⁇ 1 and n ⁇ 4 and R 2 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical and / or R 3 is hydrogen, a linear, branched, cyclic or heterocyclic unsubstituted or optionally also with Heteroatoms substituted organic radical is.
- R 3 is particularly preferably hydrogen or methyl and / or R 2 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally heteroatom-substituted organic radical.
- esters of acrylic acid or methacrylic acid are referred to.
- examples of preferably usable acrylates and methacrylates are phenyl acrylate, phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl acrylate, phenoxyethoxyethyl methacrylate, phenylthioethyl acrylate, phenylthioethyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, 1,4-bis (2-thionaphthyl) -2-butyl acrylate, 1.4 Bis (2-thionaphthyl) -2-butyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, and their ethoxylated analogues, N-carbazolyl acrylates.
- Urethane acrylates in the present context are understood as meaning compounds having at least one acrylic acid ester group and at least one urethane bond. Such compounds can be obtained, for example, by reacting a hydroxy-functional acrylate or methacrylate with an isocyanate-functional compound.
- Suitable isocyanate-functional compounds are monoisocyanates and the monomeric diisocyanates, triisocyanates and / or polyisocyanates mentioned under a).
- suitable monoisocyanates are phenyl isocyanate, the isomeric Methylthiophenylisocyanate.
- Di-, tri- or polyisocyanates are mentioned above as well as triphenylmethane-4,4 ', 4 "-triisocyanate and tris (p-isocyanatophenyl) thiophosphate or their derivatives with urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate , Biuret, oxadiazinetrione, uretdione, iminooxadiazinedione and mixtures thereof.
- Suitable hydroxy-functional acrylates or methacrylates for the preparation of urethane acrylates are, for example, compounds such as 2-hydroxyethyl (meth) acrylate, polyethylene oxide mono (meth) acrylates, polypropylene oxide mono (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly ( ⁇ -caprolactone) mono (meth) acrylates, such as Tone® M100 (Dow, Schwalbach, DE), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylic acid (2-hydroxy-3-phenoxypropyl ester), the hydroxy-functional mono-, di- or tetraacrylates of polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol,
- hydroxyl-containing epoxy (meth) acrylates known per se with OH contents of 20 to 300 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates with OH contents of 20 to 300 mg KOH / g or acrylated polyacrylates with OH Contents of 20 to 300 mg KOH / g and mixtures thereof and mixtures with hydroxyl-containing unsaturated polyesters and mixtures with polyester (meth) acrylates or mixtures of hydroxyl-containing unsaturated polyester with polyester (meth) acrylates.
- urethane acrylates are obtainable from the reaction of tris (p-isocyanatophenyl) thiophosphate and / or m-methylthiophenyl isocyanate with alcohol-functional acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and / or hydroxybutyl (meth) acrylate.
- the writing monomer further unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, vinyl ethers, propenyl ethers, allyl ether and dicyclopentadienyl units containing compounds and olefinically unsaturated compounds such.
- unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, vinyl ethers, propenyl ethers, allyl ether and dicyclopentadienyl units containing compounds and olefinically unsaturated compounds such.
- Styrene, ⁇ -methylstyrene, vinyltoluene and / or olefins such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, vinyl
- Photoinitiators which are suitable according to the invention are usually compounds which can be activated by actinic radiation and which can initiate a polymerization of the writing monomers.
- a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators.
- photoinitiators for radical, anionic, cationic or mixed type of polymerization.
- Type I photoinitiators for radical photopolymerization form free radicals upon irradiation by unimolecular bond cleavage.
- type I photoinitiators are triazines, oximes, benzoin ethers, benzil ketals, bisimidazoles, aroylphosphine oxides, sulfonium and iodonium salts.
- Radical polymerization type II photoinitiators consist of a dye as a sensitizer and a coinitiator and undergo a bimolecular reaction upon irradiation with dye-adapted light. First, the dye absorbs a photon and transfers energy to the coinitiator from an excited state. This releases the polymerization-initiating radicals by electron or proton transfer or direct hydrogen abstraction.
- type II photoinitiators are preferably used.
- Dye and coinitiator of the type II photoinitiators can either be mixed directly together with the other components of the photopolymer or else premixed with individual components.
- the dye having the isocyanate-reactive component and the coinitiator may be premixed with the isocyanate component.
- Such photoinitiator systems are in principle in the EP 0 223 587 A described and preferably consist of a mixture of one or more dyes with Ammoniumalkylarylborat (s).
- Suitable dyes which together with an ammonium alkylaryl borate form a type II photoinitiator are those disclosed in U.S. Pat WO 2012062655 described cationic dyes in combination with the anions just described there.
- Cationic dyes are preferably understood as meaning those of the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri (het) arylmethane dyes - in particular diamino- and triamino (het ) arylmethane dyes, mono-, di-, tri- and pentamethine cyanine dyes, hemicyanine dyes, externally cationic merocyanine dyes, externally cationic neutrocyanine dyes, zero methine dyes - especially naphtholactam dyes, streptocyanine dyes.
- Such dyes are for example in H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiley-VCH Verlag, 2008 . H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH publishing house, 2008 . T. Gessner, U. Mayer in Ullmann's Encyclopedia of Industrial Chemistry, Triarylmethane and Diarylmethane Dyes, Wiley-VCH Verlag, 2000 described.
- phenazine dyes particularly preferred are phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri (het) arylmethane dyes - especially diamino and triamino (het) arylmethane dyes, mono-, di-, tri- and pentamethine cyanine dyes, hemicyanine Dyes, zero methine dyes - especially naphtholactam dyes, streptocyanine dyes.
- cationic dyes are Astrazon Orange G, Basic Blue 3, Basic Orange 22, Basic Red 13, Basic Violet 7, Methylene Blue, New Methylene Blue, Azure A, 2,4-diphenyl-6- (4-methoxyphenyl) pyrylium, Safranine O. , Astraphloxin, Brilliant Green, Crystal Violet, Ethyl Violet and Thionin.
- Preferred anions are in particular C 8 - to C 25 alkane, preferably C 13 - to C 25 alkane, C 3 - to C 18 -Perfluoralkansulfonat, C 4 - to C 18 -Perfluoralkansulfonat carrying at least 3 hydrogen atoms in the alkyl chain, C 9 - to C 25 -alkanoate, C 9 - to C 25 -alkenoate, C 8 - to C 25 -alkyl sulfate, preferably C 13 - to C 25 -alkyl sulfate, C 8 - to C 25 -alkenyl sulfate, preferably C 13 - to C 25 alkenyl sulfate, C 3 to C 18 perfluoroalkyl sulfate, C 4 to C 18 perfluoroalkyl sulfate bearing at least 3 hydrogen atoms in the alkyl chain, polyether sulfates based on at least 4 equivalents of
- the anion A - of the dye has an AClogP in the range from 1 to 30, particularly preferably in the range from 1 to 12 and particularly preferably in the range from 1 to 6.5.
- the AClogP will be after J. Comput. Aid. Mol. Des. 2005, 19, 453; Calculated Virtual Computational Chemistry Laboratory, http://www.vcclab.org ,
- Suitable ammonium alkylarylborates are, for example, ( Cunningham et al., RadTech'98 North America UV / EB Conference Proceedings, Chicago, Apr. 19-22, 1998 ): Tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinapthylhexylborate, tetrabutylammonium tris (4-tert-butyl) -phenylbutylborate, tetrabutylammonium tris (3-fluorophenyl) hexylborate hexylborate ([191726-69-9], CGI 7460, product of BASF SE , Basel, Switzerland), 1-methyl-3-octylimidazolium dipentyldiphenylborate and tetrabutylammonium tris (3-chloro-4-methylphenyl
- photoinitiators it may be advantageous to use mixtures of these photoinitiators.
- the type and concentration of photoinitiator must be adapted in a manner known to the person skilled in the art. More details are for example in PKT Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, pp. 61-328 described.
- the photoinitiator comprises a combination of dyes whose absorption spectra at least partially cover the spectral range from 400 to 800 nm with at least one co-initiator adapted to the dyes.
- At least one suitable for a laser light color of blue, green and red photoinitiator is included in the photopolymer formulation.
- the photopolymer formulation contains at least two laser light colors selected from blue, green and red each contain a suitable photoinitiator.
- the photopolymer formulation in each case contains a suitable photoinitiator for each of the laser light colors blue, green and red.
- the photopolymer formulation additionally contains monomeric urethanes as additives, wherein the urethanes may be substituted in particular with at least one fluorine atom.
- the urethanes may preferably have the general formula (III) have in which m ⁇ 1 and m ⁇ 8 and R 4 , R 5 and R 6 are linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radicals and / or R 5 , R 6 are independently hydrogen, wherein preferably at least one of the radicals R 4 , R 5 , R 6 is substituted by at least one fluorine atom and more preferably R 4 is an organic radical having at least one fluorine atom.
- R 5 is particularly preferably a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by heteroatoms such as fluorine organic radical.
- the invention likewise provides a holographic medium comprising matrix polymers, writing monomers and photoinitiators, the writing monomers comprising a compound of the formula (I) according to the invention.
- the matrix polymers are crosslinked, preferably three-dimensionally crosslinked, and very particularly preferably three-dimensionally crosslinked polyurethanes.
- the holographic medium comprises at least one fluorourethane as an additive.
- the holographic medium may be a film which may preferably have a film thickness of from 0.5 ⁇ m to 200 ⁇ m, more preferably from 0.8 ⁇ m to 50 ⁇ m, and particularly preferably from 1 ⁇ m to 25 ⁇ m.
- At least one hologram can also be imprinted in the holographic medium.
- Holograms can be imprinted into the holographic media according to the invention by appropriate exposure processes for optical applications in the entire visible and near UV range (300-800 nm).
- Visual holograms include all holograms that can be recorded by methods known to those skilled in the art. These include in-line (Gabor) holograms, off-axis holograms, full-aperture transfer holograms, white-light transmission holograms, denisy-holograms, off-axis reflection holograms, edge-lit holograms, and holographic stereograms. Denisyuk holograms, transmission holograms.
- Possible optical functions of the holograms correspond to the optical functions of light elements such as lenses, mirrors, deflection mirrors, filters, diffusers, diffractive elements, diffusers, light guides, waveguides, projection screens and / or masks. Also, combinations of these optical functions may be unified independently in a hologram. Frequently, these optical elements exhibit frequency selectivity depending on how the holograms were exposed and the dimensions of the hologram.
- holographic images or representations can also be produced by means of the media according to the invention, for example for personal portraits, biometric representations in security documents, or generally for images or image structures for advertising, security labels, trademark protection, branding, labels, design elements, decorations, illustrations, trading cards , Images and the like, as well as images that can represent digital data, including in combination with the previously presented products.
- Holographic images can have the impression of a three-dimensional image, but they can also represent image sequences, short films or a number of different objects, depending on which angle, with which (even moving) light source, etc., this is illuminated. Because of these diverse design possibilities, holograms, in particular volume holograms, represent an attractive technical solution for the above-mentioned application.
- the present invention furthermore relates to the use of a holographic medium according to the invention for recording in-line, off-axis, full-aperture transfer, white-light transmissions, denisyuk, off-axis reflection or edge-lit holograms and holographic stereograms, in particular for the production of optical elements, images or image representations.
- a process for producing a holographic medium using a photopolymer formulation according to the invention is a process for producing a holographic medium using a photopolymer formulation according to the invention.
- the photopolymer formulations can be used in particular for producing holographic media in the form of a film.
- a layer of a material or composite material transparent to light in the visible spectral range is coated on one or both sides and optionally a cover layer applied to the photopolymer layer (s).
- Preferred materials or composite materials of the carrier are based on polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene, polypropylene, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, polyepoxides, polysulfone, cellulose triacetate (CTA), polyamide, polymethyl methacrylate, polyvinyl chloride, polyvinyl butyral or polydicyclopentadiene or mixtures thereof. Most preferably, they are based on PC, PET and CTA. Composite materials may be film laminates or co-extrudates.
- Preferred composite materials are duplex and triplex films constructed according to one of the schemes A / B, A / B / A or A / B / C.
- the materials or composite materials of the carrier may be unilaterally or bilaterally anti-adhesive, antistatic, hydrophobed or hydrophilated.
- the modifications mentioned serve on the photopolymer layer side facing the purpose that the photopolymer layer can be detached from the carrier nondestructive.
- a modification of the side of the carrier remote from the photopolymer layer serves to ensure that the media according to the invention satisfy special mechanical requirements, e.g. when processing in roll laminators, especially in roll-to-roll processes.
- Another object of the invention is also a display comprising a holographic medium according to the invention.
- OH number The indicated OH numbers were determined according to DIN 53240-2.
- NCO value The indicated NCO values (isocyanate contents) were determined in accordance with DIN EN ISO 11909.
- Solids content The stated solids contents were determined according to DIN EN ISO 3251.
- the media prepared as described in the section "Preparation of Media for Determining Holographic Properties" were measured by means of a measuring arrangement according to FIG. 1
- the holographic properties of a He-Ne laser beam (emission wavelength 633 nm) were converted into a parallel homogeneous beam by means of the spatial filter (SF) and together with the collimation lens (CL).
- the final cross sections of the signal and reference beam are defined by the iris diaphragms (I).
- the diameter of the iris aperture is 0.4 cm.
- the polarization-dependent beam splitters (PBS) divide the laser beam into two coherent identically polarized beams.
- the power of the reference beam was set to 0.5 mW and the power of the signal beam to 0.65 mW.
- the performances were determined with the semiconductor detectors (D) with the sample removed.
- the angle of incidence ( ⁇ 0 ) of the reference beam is - 21.8 °
- the angle of incidence ( ⁇ 0 ) of the signal beam is 41.8 °.
- the angles are measured from the sample standard to the beam direction. According to FIG. 1 Therefore, ⁇ 0 has a negative sign and ⁇ 0 has a positive sign.
- the interference field of the two overlapping beams produced a grid of bright and dark stripes perpendicular to the bisector of the two beams incident on the sample (reflection hologram).
- the stripe distance A also called the grating period, in the medium is ⁇ 225 nm (the refractive index of the medium is assumed to be ⁇ 1.504).
- HMT Holographic Media Tester
- the written holograms have now been read out in the following way.
- the shutter of the signal beam remained closed.
- the shutter of the reference beam was open.
- the iris diaphragm of the reference beam was closed to a diameter ⁇ 1 mm. It was thus achieved that for all rotation angles ( ⁇ ) of the medium, the beam was always located completely in the previously written hologram.
- the turntable computer controlled controlled the angular range from Q min to Q max with an angle increment of 0.05 °.
- ⁇ is measured from the sample standard to the reference direction of the turntable.
- ⁇ recording 0 °.
- ⁇ 0 -31.8 °.
- the powers of the beam transmitted in the zeroth order were measured by means of the corresponding detector D and the powers of the beam deflected to the first order by means of the detector D.
- P D is the power in the detector of the diffracted beam and P T is the power in the detector of the transmitted beam.
- the Bragg curve which describes the diffraction efficiency ⁇ as a function of the angle of rotation ⁇ , of the written hologram was measured and stored in a computer.
- the intensity transmitted in the zeroth order was also recorded against the angle of rotation ⁇ and stored in a computer.
- the maximum diffraction efficiency (DE ⁇ max ) of the hologram, ie its peak value, was determined during ⁇ reconstruction . It may be necessary to change the position of the detector of the diffracted beam to determine this maximum value.
- the refractive index contrast ⁇ n and the thickness d of the photopolymer layer has now been determined by means of the coupled wave theory (cf. H. Kogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9 Page 2909 - Page 2947 ) to the measured Bragg curve and the angle profile of the transmitted intensity. It should be noted that due to the thickness shrinkage occurring due to the photopolymerization, the strip spacing ⁇ 'of the hologram and the orientation of the strips (slant) can deviate from the strip spacing ⁇ of the interference pattern and its orientation.
- ⁇ 'and ⁇ ' correspond to the angles ⁇ 0 and ⁇ 0 of the interference field when writing the hologram, but measured in the medium and valid for the lattice of the hologram (after thickness shrinkage).
- n is the average refractive index of the photopolymer and was set to 1,504.
- ⁇ is the wavelength of the laser light in a vacuum.
- FIG. 2 shows the measured transmitted power P T (right y -axis) plotted against the angular detection ⁇ as a solid line, the measured diffraction efficiency ⁇ (left y- axis) plotted as solid circles against the angular detection ⁇ (as far as the finite size of the detector allowed) and the adaptation of the Kogelnik theory as a dashed line (left y- axis).
- the detector for the diffracted light can detect only a finite angular range
- the Bragg curve of broad fathoms (small d ') in an ⁇ -scan is not fully detected but only the central area, with appropriate detector positioning. Therefore, the complementary to the Bragg curve shape of the transmitted intensity to adjust the layer thickness d 'is additionally used.
- FIG. 2 shows the representation of the Bragg curve ⁇ according to the Coupled Wave Theory (dashed line), the measured diffraction efficiency (filled circles) and the transmitted power (black solid line) against the Winkelduning ⁇ .
- this procedure may be repeated several times for different exposure times t on different media to determine at what average absorbed dose of the incident laser beam when writing the hologram DE into the saturation value passes.
- the powers of the partial beams have been adjusted so that the same power density is achieved in the medium at the angles ao and ⁇ 0 used.
- BINOL (+/-) - 1,1'-Bi (2-naphthol) [602-09-5] is available from ABCR GmbH & Co. KG, Düsseldorf, Germany.
- 6,6'-dibromo-1,1'-bi-naphthalene-2,2-diol [80655-81-8] is available from ABCR GmbH & Co. KG, Düsseldorf, Germany.
- 7-methoxy-2-naphthol [5060-82-2] is available from Aldrich Chemie, Steinheim, Germany.
- Methyl-3-hydroxy-2-naphthoate [883-99-8] is available from ABCR GmbH & Co. KG, Düsseldorf, Germany.
- 6-Bromo-2-naphthol [15231-91-1] is available from ABCR GmbH & Co. KG, Düsseldorf, Germany.
- 6-cyano-2-naphthol [52927-22-7] is available from ABCR GmbH & Co. KG, Düsseldorf, Germany.
- 2- (phenylthio) phenyl isocyanate [13739-55-4] is available from ABCR GmbH & Co. KG, Düsseldorf, Germany.
- CGI-909 Tetrabutylammonium tris (3-chloro-4-methylphenyl) (hexyl) borate, [1147315-11-4] is a product manufactured by CIBA Inc., Basel, Switzerland.
- Example 1 2 - [( ⁇ [2 ' - ( ⁇ [2- (Acryloyloxy) ethyl] carbamoyl ⁇ oxy) -1 , 1'-binaphthyl-2-yl] oxy ⁇ carbonyl) amino] ethyl methacrylate
- Example 5 (6,6'-Dicyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate
- Example 10 2 - ⁇ [( ⁇ 2 '- [(Hexylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl ⁇ oxy) carbonyl] amino ⁇ ethyl methacrylate
- Example 11 2 - ⁇ [( ⁇ 2 '- [(Hexylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl ⁇ oxy) carbonyl] amino ⁇ ethyl acrylate
- Example 12 2 - ⁇ [( ⁇ 2 '- [(Hexylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl ⁇ oxy) carbonyl] amino ⁇ ethyl acrylate
- Example 13 2 - [( ⁇ [2 '- ( ⁇ [3- (Methylsulfanyl) phenyl] carbamoyl ⁇ oxy) -1,1'-binaphthyl-2-yl] oxy ⁇ carbonyl) amino] ethyl acrylate
- Example 14 2 - ⁇ [( ⁇ 2 '- [(Hexylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl ⁇ oxy) carbonyl] amino ⁇ ethyl methacrylate
- Example 15 2 - [( ⁇ [2 '- ( ⁇ [3- (Methylsulfanyl) phenyl] carbamoyl ⁇ oxy) -1,1'-binaphthyl-2-yl] oxy ⁇ carbonyl) amino] ethyl acrylate
- Example 16 2 - ⁇ [( ⁇ 2 '- [(Hexylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl ⁇ oxy) carbonyl] amino ⁇ ethyl methacrylate
- Example 17 2 - ⁇ [( ⁇ 2 '- [(1-Naphthylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl ⁇ oxy) carbonyl] amino ⁇ ethyl acrylate
- Example 18 2 - ⁇ [( ⁇ 2 '- [(1-Naphthylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl ⁇ oxy) carbonyl] amino ⁇ ethyl methacrylate
- Example 21 (2,2,4-trimethylhexane-1,6-diyl) bis (carbamoyloxy-1,1'-binaphthyl-2 ', 2-diyloxycarbonyliminoethane-2,1-diyl) -bisacrylate
- Example 22 (2,2,4-trimethylhexane-1,6-diyl) bis (carbamoyloxy-1,1'-binaphthyl-2 ', 2-diyloxycarbonyliminoethane-2,1-diyl) -bis (2-methylacrylate)
- Example 23 2 - ( ⁇ [(2 '- ⁇ [(3 - ⁇ [( ⁇ [2' - ( ⁇ [2- (acryloyloxy) ethyl] carbamoyl ⁇ oxy) -1,1'-binaphthyl-2-yl ] oxy ⁇ carbonyl) amino] methyl ⁇ -3,5,5-trimethylcyclohexyl) carbamoyl] -oxy ⁇ -1,1'-binaphthyl-2-yl) oxy] carbonyl ⁇ amino) ethyl acrylate
- Example 24 2 - ( ⁇ [(2 '- ⁇ [(3 - ⁇ [( ⁇ [2' - ( ⁇ [2- (methacryloyloxy) ethyl] carbamoyl ⁇ oxy) -1,1'-binaphthyl-2-yl ] oxy ⁇ carbonyl) amino] methyl ⁇ -3,5,5-trimethylcyclohexyl) carbamoyl] oxy ⁇ -1,1'-binaphthyl-2-yl) oxy] carbonyl ⁇ amino) ethyl methacrylate)
- Example 25 (6-Bromo-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate
- Example 26 (6-Bromo-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate)
- Example 27 (6-cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate
- Example 28 (6-cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate)
- Example 29 (6-Bromo-6'-cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate
- Example media II-IX were prepared as described under Example Medium I. It was - as listed in Table 1 - Example 1 replaced by the example listed in each row in the same weight proportion.
- the determination of the refractive index modulation ⁇ n in a holographically exposed photopolymer according to the method described above succeeds most accurately when the diffraction efficiency is not completely saturated but close to 100%.
- the diffraction efficiency DE depends on the product of ⁇ n and the layer thickness d of the photopolymer.
- a selected example (Example 3) was processed in a continuous coating plant to a photopolymer.
- Both components were then each promoted and degassed by the metering devices 2a and 2b in the ratio of 16.3 to 1 (reservoir 1a to 1b) to the vacuum degassing devices 3a and 3b. From here, they were then each passed through the filters 4a and 4b in the static mixer 5, in which the mixing of the components for photopolymer formulation was carried out. The resulting liquid mass was then fed to the coater 6 in the dark.
- the coating device 6 in the present case was a slot nozzle known to the person skilled in the art. Alternatively, however, a doctor blade system or a roll application system can also be used. With the help of the coating device 6, the photopolymer formulation was applied at a processing temperature of 20 ° C on a carrier substrate 8 in the form of a 36 micron thick polyethylene terephthalate and dried for 5.8 minutes at a crosslinking temperature of 80 ° C in a convection dryer 7. In this case, a medium in the form of a film was obtained, which was then provided with a 40 micron polyethylene film as the cover layer 9 and wound up.
- the achieved layer thickness of the film is 6 - 8 microns.
- Example media Example according to formula (I) .DELTA.n I 1 0043 II 3 0050 III 4 0051 IV 6 0050 V 7 0040 VI 8th 0040 VII 19 0038 VIII 20 0037 IX 22 0038 X 3 0060 Comparison medium .DELTA.n VI 0035 V-II 0035
- the values found for the example media I to IX show that the compounds of the formula (I) according to the invention used in the photopolymer formulations are very suitable for use in holographic media with very high refractive index modulation An.
- the comparative media V-1 and V-2 have no inventive Compound of formula (I) and have lower values for ⁇ n in holographic media. It can be shown with the example medium X that the compounds of the formula (I) used according to the invention have a very high refractive index modulation ⁇ n.
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Description
Die Erfindung betrifft Naphthylacrylate, die insbesondere als Schreibmonomere in Photopolymer-Formulierungen für holographische Medien verwendet werden können. Darüber hinaus sind eine Photopolymer-Formulierung, umfassend Matrixpolymere, Schreibmonomere und Photoinitiatoren, wobei die Schreibmonomere ein erfindungsgemäßes Naphthylacrylat umfassen, ein holographisches Medium, umfassend Matrixpolymere, Schreibmonomere und Photoinitiatoren, wobei die Schreibmonomere ein erfindungsgemäßes Naphthylacrylat umfassen, sowie ein Display umfassend ein erfindungsgemäßes holographisches Medium Gegenstände der Erfindung.The invention relates to naphthyl acrylates, which can be used in particular as writing monomers in photopolymer formulations for holographic media. In addition, a photopolymer formulation comprising matrix polymers, random monomers and photoinitiators, the random monomers comprising a naphthyl acrylate of the invention, a holographic medium comprising matrix polymers, random monomers and photoinitiators, the random monomers comprising a naphthyl acrylate of the invention and a display comprising a holographic medium of the invention Objects of the invention.
Photopolymer-Formulierungen sind im Stand der Technik bekannt. So ist beispielsweise in der
Hochbrechende Acrylate sind in der Lage, Brechungsindexgitter mit hoher Amplitude zwischen Bereichen mit niedrigem Brechungsindex und Bereichen mit hohem Brechungsindex zu erzeugen und damit in Photopolymeren Hologramme mit hohem DE und hohem Δn zu ermöglichen. Dabei ist zu beachten, dass die DE vom Produkt aus Δn und der Photopolymerschichtdicke d abhängt. Je größer das Produkt, desto größer die mögliche DE (für Reflexionshologramme). Die Breite des Winkelbereiches bei dem das Hologramm z.B. bei monochromatischer Beleuchtung sichtbar (rekonstruiert) wird, hängt nur von der Schichtdicke d ab.High refractive index acrylates are capable of producing high amplitude refractive index gratings between low refractive index regions and high refractive index regions, thereby allowing high DE and high Δn holograms in photopolymers. It should be noted that the DE depends on the product of Δn and the photopolymer layer thickness d depends. The larger the product, the larger the potential DE (for reflection holograms). The width of the angular range at which the hologram is visible (reconstructed), for example in the case of monochromatic illumination, depends only on the layer thickness d.
Bei Beleuchtung des Hologramms mit z.B. weißem Licht hängt die Breite des spektralen Bereiches, der zur Rekonstruktion des Hologramms beitragen kann, ebenfalls nur von der Schichtdicke d ab. Dabei gilt je kleiner d desto größer die jeweiligen Akzeptanzbreiten. Will man daher helle und leicht sichtbare Hologramme herstellen, ist ein hohes Δn und eine geringe Dicke d anzustreben und zwar so, dass die DE möglichst groß wird. Das heißt je höher Δn wird, desto mehr Freiraum zur Gestaltung der Schichtdicke d für helle Hologramme erreicht man ohne Verlust an DE. Daher kommt der Optimierung von Δn bei der Optimierung von Photopolymer-Formulierungen eine herausragenden Bedeutung zu (
Aufgabe der vorliegenden Erfindung war es, eine Verbindung bereitzustellen, die sich als Schreibmonomer zur Herstellung von holographischen Medien mit hohem Brechungsindexkontrast (Δn) eignet. Diese Aufgabe ist durch eine Verbindung der Formel (I)
- a) die an wenigstens einem der
1, 2, 3, 4, 5, 6, 7, 8 mit einem Rest RArcyl der Formel (II) substituiert ist,Kohlenstoffatome - R1
- Wasserstoff oder eine (C1-C6)-Alkylgruppe,
- X
- eine Carbonamid (-C(O)N-) oder eine Carbonester (-C(O)O-) oder eine Sulfonamid (-SO2N-) Gruppe,
- Y
- ein gesättigter oder ungesättigter oder linearer oder verzweigter gegebenenfalls substituierter 2-10 C-Atome aufweisender Rest oder ein bis zu fünf (-CH2-CH2-O-)- oder (-C(CH3)H-CH2-O-)-Gruppen aufweisender Polyether oder ein bis zu fünf Stickstoff-Atome aufweisendes Polyamin, und
- Z
- Sauerstoff oder Schwefel ist,
- b) und die Verbindung der Formel (I) an wenigstens einem
1, 2, 3, 4, 5, 6, 7, 8 mit einem Rest der Formel (III) substituiert istweiteren Kohlenstoffatom
die Kohlenstoffatome der Verbindung der Formel (III) jeweils unabhängig mit Wasserstoff, Halogen, einer Cyano-Gruppe, einer Nitro-Gruppe oder einer gegebenenfalls substituierten Alkyl-, Alkenyl-, Alkinyl-, Aralkyl-, Aryl- oder Heteroaryl-Gruppe oder einer gegebenenfalls substituierten Alkylthio-Gruppe oder einer beliebig substituierten Carbamoyl-Gruppe, die auch verbrückend an einen Rest der Formel (I) gebunden sein kann, oder einer Trifluormethyl-Gruppe oder einer Trifluormethoxy-Gruppe oder einem Rest RArcyl' der Formel (IV),- R1'
- Wasserstoff oder eine (C1-C6)-Alkylgruppe,
- X'
- eine Carbonamid (-C(O)N-) oder eine Carbonester (-C(O)O-) oder eine Sulfonamid (-SO2N-) Gruppe,
- Y'
- ein gesättigter oder ungesättigter oder linearer oder verzweigter gegebenenfalls substituierter 2-10 C-Atome aufweisender Rest oder ein bis zu fünf (-CH2-CH2-O-)- oder (-C(CH3)H-CH2-O-)-Gruppen aufweisender Polyether oder ein bis zu fünf Stickstoff-Atome aufweisendes Polyamin, und
- Z'
- Sauerstoff oder Schwefel ist,
- c) die übrigen Kohlenstoffatome der Verbindung der Formel (I) jeweils unabhängig mit Wasserstoff, Halogen, einer Cyano-Gruppe, einer Nitro-Gruppe oder einer gegebenenfalls substituierten Alkyl-, Alkenyl-, Alkinyl-, Aralkyl-, Aryl- oder Heteroaryl-Gruppe oder einer gegebenenfalls substituierten Alkylthio-Gruppe oder einer Trifluormethyl-Gruppe oder einer Trifluormethoxy-Gruppe substituiert sind, gelöst.
- a) is substituted at at least one of
1, 2, 3, 4, 5, 6, 7, 8 with a radical R Arcyl of formula (II),carbon atoms - R 1
- Hydrogen or a (C 1 -C 6 ) -alkyl group,
- X
- a carbonamide (-C (O) N-) or a carboxylic ester (-C (O) O-) or a sulfonamide (-SO 2 N-) group,
- Y
- a saturated or unsaturated or linear or branched optionally substituted 2-10 C-atoms containing radical or one to five (-CH 2 -CH 2 -O -) - or (-C (CH 3 ) H-CH 2 -O- ) Polyethers or a polyamine having up to five nitrogen atoms, and
- Z
- Oxygen or sulfur is,
- b) and the compound of formula (I) is substituted on at least one
1, 2, 3, 4, 5, 6, 7, 8 with a radical of formula (III)further carbon atom
the carbon atoms of the compound of formula (III) each independently with hydrogen, halogen, a cyano group, a nitro group or an optionally substituted alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl group or optionally substituted alkylthio group or an arbitrarily substituted carbamoyl group, which may also be bridged to a radical of the formula (I) bonded, or a trifluoromethyl group or a trifluoromethoxy group or a radical R Arcyl 'of formula (IV),- R 1 '
- Hydrogen or a (C 1 -C 6) -alkyl group,
- X '
- a carbonamide (-C (O) N-) or a carboxylic ester (-C (O) O-) or a sulfonamide (-SO 2 N-) group,
- Y '
- a saturated or unsaturated or linear or branched optionally substituted 2-10 C-atoms containing radical or one to five (-CH 2 -CH 2 -O -) - or (-C (CH 3 ) H-CH 2 -O- ) Polyethers or a polyamine having up to five nitrogen atoms, and
- Z '
- Oxygen or sulfur is,
- c) the remaining carbon atoms of the compound of formula (I) each independently with hydrogen, halogen, a cyano group, a nitro group or an optionally substituted alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl group or an optionally substituted alkylthio group or a trifluoromethyl group or a trifluoromethoxy group are dissolved.
So wurde überraschenderweise gefunden, dass sich das Verbindungen der Formel (I) sehr gut als Schreibmonomer zur Herstellung von holographischen Medien mit sehr hohem Brechungsindexkontrast (Δn) und hoher optischer Qualität eignet.Thus, it has surprisingly been found that the compound of formula (I) is very suitable as a writing monomer for the production of holographic media with a very high refractive index contrast (Δn) and high optical quality.
Die erfindungsgemäßen Verbindungen der Formel (I) können beispielsweise in der folgenden Weise hergestellt werden: Durch oxidative Kupplung von Naphtholen können bezüglich Formel (I) und Formel (III) symmetrische oder un-symmetrische Bis-Naphthole hergestellt und gegebenenfalls präparativ getrennt werden, die dann in einem nachfolgenden Syntheseschritt mit OH-reaktiven Verbindungen zu Acrylaten umgesetzt werden können. Es ist ebenfalls möglich, kommerziell erhältliche Bis-Naphthole mit OH-reaktiven Verbindungen zu Acrylaten umzusetzen. Darüber hinaus können auch verbrückende zwei- oder höherfunktionelle OH-reaktive Bausteine zur Kupplung von zwei Bis-Naphtholen eingesetzt werden und die erhaltenen Produkte dann weiter zu Acrylaten der Formel (I) umgesetzt werden.The compounds of the formula (I) according to the invention can be prepared, for example, in the following manner: By oxidative coupling of naphthols with respect to formula (I) and formula (III) symmetrical or non-symmetrical bis-naphthols can be prepared and optionally separated by preparative means, which then in a subsequent synthesis step with OH-reactive compounds to acrylates can be implemented. It is also possible to react commercially available bis-naphthols with OH-reactive compounds to give acrylates. In addition, it is also possible to use bridging two- or higher-functional OH-reactive building blocks to couple two bis-naphthols and then to further convert the resulting products to acrylates of the formula (I).
Gemäß einer ersten bevorzugten Ausführungsform der erfindungsgemäßen Verbindung ist vorgesehen, dass sie an dem Kohlenstoffatom der Position 5 in der Formel (I) mit dem Rest der Formel (III) substituiert ist, wobei der Rest der Formel (III) bevorzugt über das Kohlenstoffatom der Position 8' an das Kohlenstoffatom der Position 5 gebunden sein kann.According to a first preferred embodiment of the compound according to the invention is provided that it is substituted at the carbon atom of
Ebenfalls bevorzugt ist, wenn die Verbindung an dem Kohlenstoffatom der Position 6 in der Formel (I) mit dem Rest RArcyl der Formel (II) substituiert ist.Is also preferred if the connection to the
Vorteilhaft ist auch, wenn der Rest der Formel (III) an dem Kohlenstoffatom der Position 7' mit dem Rest RArcyl' der Formel (IV) substituiert ist.It is also advantageous if the radical of formula (III) is substituted on the carbon atom of position 7 'by the radical R ' of the formula (IV).
Bei einer weiteren bevorzugten Ausführungsform der Erfindung ist vorgesehen, dass in dem Rest RArcyl X für Carbonamid und / oder in dem Rest RArcyl' X für Carbonamid steht.In a further preferred embodiment of the invention, it is provided that in the radical R, Arcyl X stands for carbonamide and / or in the radical R, Arcyl ' X stands for carbonamide.
Weiterhin vorteilhaft ist auch, wenn in dem Rest RArcyl R1 für Wasserstoff oder einen CH3-Rest und / oder in dem Rest RArcyl' R1' für Wasserstoff oder einen CH3-Rest steht.It is also advantageous if in the radical R Arcyl R 1 is hydrogen or a CH 3 radical and / or in the radical R Arcyl ' R 1 ' is hydrogen or a CH 3 radical.
Darüber hinaus kann vorzugsweise in dem Rest RArcyl Y ein -CH2-CH2-Rest und / oder in dem der Rest RArcyl' Y' ein -CH2-CH2-Rest sein.In addition, preferably in the radical R, Arcyl Y may be a -CH 2 -CH 2 radical and / or in which the radical R may be a -CH 2 -CH 2 radical.
Bevorzugt ist auch, wenn Z und / oder Z' Sauerstoff ist.It is also preferred if Z and / or Z 'is oxygen.
Ganz besonders bevorzugt ist, wenn Z und / oder Z' Sauerstoff ist und X und / oder X' eine Carbonamid-Gruppe ist.Very particularly preferred is when Z and / or Z 'is oxygen and X and / or X' is a carbonamide group.
Insbesondere bevorzugt ist die erfindungsgemäße Verbindung der Formel (I) aus der Gruppe der folgenden Substanzen ausgewählt: 2-[({[2'-({[2-(Acryloyloxy)ethyl]carbamoyl}oxy)-1,1'-binaphthyl-2-yl]oxy}carbonyl)amino]ethyl methacrylat, Dimethyl 2,2'-bis({[2-(methacryloyloxy)ethyl]carbamoyl}oxy)-1,1'-binaphthyl-3,3'-dicarboxylat, Diethyl 2,2'-bis({[2-(methacryloyloxy)ethyl]carbamoyl}oxy)-1,1'-binaphthyl-3,3 '-dicarboxylat, 1,1'-Binaphthyl-2,2'-diylbis(oxycarbonyliminoethan-2,1-diyl)bisacrylat, 1,1'-Binaphthyl-2,2'-diylbis(oxycarbonyliminoethan-2,1-diyl)bis(2-methylacrylat), (6,6'-Dicyano-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6,6'-Difluoro-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6,6'-Dichloro-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat(6,6'-Dibromo-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6,6'-Diiodo-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, Difluoro-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat), (6,6'-Dichloro-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat), (6,6'-Dibromo-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat), (6,6'-Diiodo-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat), (7,7'-Dimethoxy-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (7,7'-Diethoxy-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, 2-{[({2'-[(Hexylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylat, 2-{[({2'-[(Butylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylat, 2-{[({2'-[(Hexylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl 2-methylacrylat, 2-{[({2'-[(Butylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl2-methylacrylat, 2-{[({2'-[(Hexylcarbamoyl)-oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylat, 2-{[({2'-[(Hexylcarbamoyl)-oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl 2-methylacrylat, 2-{[({2'-[(Hexylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylat, 2-{[({2'-[(Hexylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl)oxy)carbonyl]amino}ethyl 2-methylacrylat, 2-{[({2'-[(Butylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylat, 2-{[({2'-[(Butylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl 2-methylacrylat, 2-[({[2'-({[3-(Methylsulfanyl)phenyl]carbamoyl}oxy)-1,1'-binaphthyl-2-yl]oxy}-carbonyl)amino]ethyl acrylat, 2-[({[2'-({[3-(Methylsulfanyl)phenyl]carbamoyl}oxy)-1,1'-binaphthyl-2-yl]oxy}carbonyl)amino]ethyl methacrylat, 2-[({[2'-({[2-(Methylsulfanyl)phenyl]carbamoyl}oxy)-1,1'-binaphthyl-2-yl]oxy}carbonyl)amino] ethyl acrylat, 2-[({[2'-({[2-(Methylsulfanyl)phenyl]carbamoyl}oxy)-1,1'-binaphthyl-2-yl]oxy}-carbonyl)amino]ethyl methacrylat, 2-[({[2'-({[4-(Methylsulfanyl)phenyl]carbamoyl}oxy)-1,1'-binaphthyl-2-yl]oxy}carbonyl)amino]ethyl acrylat, 2-[({[2'-({[4-(Methylsulfanyl)phenyl]carbamoyl}oxy)-1,1'-binaphthyl-2-yl]oxy}carbonyl)amino]ethyl methacrylat, 2-{[({2'-[(1-Naphthylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethyl acrylat, 2-{[({2'-[(1-Naphthylcarbamoyl)oxy]-1,1'-binaphthyl-2-yl}oxy)carbonyl]amino}ethylmethacrylat, Hexan-1,6-diylbis(carbamoyloxy-1,1'-binaphthyle-2',2-diyloxycarbonyliminoethan-2,1-diyl) bisacrylat, Hexan-1,6-diylbis(carbamoyloxy-1,1'-binaphthyle-2',2-diyloxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat), (2,2,4-Trimethylhexane-1,6-diyl)bis(carbamoyloxy-1,1'-binaphthyl-2',2-diyloxycarbonyliminoethane-2,1-diyl)-bisacrylat, (2,2,4-Trimethylhexane-1,6-diyl)bis-(carbamoyloxy-1,1'-binaphthyl-2',2-diyloxycarbonyliminoethane-2,1-diyl)-bis(2-methylacrylat), 2-({[(2'-{[(3-{[({[2'-({[2-(Acryloyloxy)ethyl]carbamoyl}oxy)-1,1'-bi-naphthyl-2-yl]oxy}carbonyl)amino]methyl}-3,5,5-trimethylcyclohexyl)carbamoyl]-oxy}-1,1'-binaphthyl-2-yl)oxy]carbonyl}amino)ethyl acrylat, 2-({[(2'-{[(3-{[({[2'-({[2-(Methacryloyloxy)ethyl]carbamoyl}oxy)-1,1'-binaphthyl-2-yl]oxy}carbonyl)amino]methyl}-3,5,5-trimethylcyclohexyl)¬carbamoyl]oxy}-1,1'-binaphthyl-2-yl)oxy]carbonyl}amino)ethyl methacrylat), (6-Fluor-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6-Fluor-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis (2-methylacrylat), (6-Chlor-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6-Chlor-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis (2-methylacrylat), (6-Brom-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6-Brom-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis (2-methylacrylat), (6-Iod-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6-Iod-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis (2-methylacrylat), (6-Cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6-Cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat), (6-Fluor-6'-cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6-Fluor-6'-cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat), (6-Chlor-6'-cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl)bisacrylat, (6-Chlor-6'-cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat), (6-Brom-6'-cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6-Brom-6'-cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat), (6-Iod-6'-cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bisacrylat, (6-Iod-6'-cyan-1,1'-binaphthyl-2,2'-diyl)bis(oxycarbonyliminoethan-2,1-diyl) bis(2-methylacrylat).With particular preference the compound of the formula (I) according to the invention is selected from the group of the following substances: 2 - [({[2 '- ({[2- (acryloyloxy) ethyl] carbamoyl} oxy) -1,1'-binaphthyl- 2-yl] oxy} carbonyl) amino] ethyl methacrylate, dimethyl 2,2'-bis ({[2- (methacryloyloxy) ethyl] carbamoyl} oxy) -1,1'-binaphthyl-3,3'-dicarboxylate, diethyl 2,2'-bis ({[2- (methacryloyloxy) ethyl] carbamoyl} oxy) -1,1'-binaphthyl-3,3'-dicarboxylate, 1,1'-binaphthyl-2,2'-diylbis (oxycarbonyliminoethane -2,1-diyl) bisacrylate, 1,1'-binaphthyl-2,2'-diylbis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6,6'-dicyano-1,1 '-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (6,6'-difluoro-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2, 1-diyl) bisacrylate, (6,6'-dichloro-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate (6,6'-dibromo-1,1 '-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (6,6'-diiodo-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2 ,1 -diyl) bisacrylate, difluoro-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6,6'-dichloro-1,1 '-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6,6'-dibromo-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6,6'-diiodo-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (7,7'-dimethoxy-1,1 '-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (7,7'-diethoxy-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2 , 1-diyl) bisacrylate, 2 - {[({2 '- [(hexylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl} oxy) carbonyl] amino} ethyl acrylate, 2 - {[({2 '- [(butylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl} oxy) carbonyl] amino} ethyl acrylate, 2 - {[({2' - [(hexylcarbamoyl) oxy] -1,1'- binaphthyl-2-yl} oxy) carbonyl] amino} ethyl 2-methylacrylate, 2 - {[({2 '- [(butylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl} oxy) carbonyl] amino} ethyl 2-methyl acrylate, 2 - {[({2 '- [(hexylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl} oxy) carbonyl] amino} ethyl acrylate, 2 - {[({2'- [(Hexylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl} oxy) carbonyl] amino} ethyl 2-methylacrylate, 2 - {[({2 '- [(hexylcarbamoyl) oxy] -1,1' -binaphthyl-2-yl} oxy) carbonyl] amino} ethyl acrylate, 2 - {[({2 '- [(hexylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl) oxy) carbonyl] amino} ethyl 2-methyl acrylate, 2- { [({2 '- [(Butylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl} oxy) carbonyl] amino} ethyl acrylate, 2 - {[({2' - [(Butylcarbamoyl) oxy] -1 , 1'-binaphthyl-2-yl) oxy) carbonyl] amino} ethyl 2-methylacrylate, 2 - [({[2 '- ({[3- (methylsulfanyl) phenyl] carbamoyl} oxy) -1,1'- binaphthyl-2-yl] oxy} carbonyl) amino] ethyl acrylate, 2 - [({[2 '- ({[3- (methylsulfanyl) phenyl] carbamoyl} oxy) -1,1'-binaphthyl-2-yl ] oxy} carbonyl) amino] ethyl methacrylate, 2 - [({[2 '- ({[2- (methylsulfanyl) phenyl] carbamoyl} oxy) -1,1'-binaphthyl-2-yl] oxy} carbonyl) amino ] ethyl acrylate, 2 - [({[2 '- ({[2- (methylsulfanyl) phenyl] carbamoyl} oxy) -1,1'-binaphthyl-2-yl] oxy} -carbonyl) amino] ethyl methacrylate, 2 - [({[2 '- ({[4- (Methylsulfanyl) phenyl] carbamoyl} oxy) -1,1'-binaphthyl-2-yl] oxy} carbonyl) amino] ethyl acrylate, 2 - [({[2 '- ({[4- (Methylsulfanyl) phenyl] carbamoyl} oxy) -1,1'-binaphthyl-2-yl] oxy} carbonyl) amino] ethyl methacrylate, 2 - {[({2' - [(1- Naphthylcarbamoyl) oxy] -1,1'-binaphthyl-2-yl} oxy) carbonyl] amino} ethyl acrylate, 2 - {[({2 '- [(1-naphthylcarbamoyl) oxy] -1,1'-binaphthyl- 2-yl} oxy) carbonyl] amino ethylmethacrylate, hexane-1,6-diylbis (carbamoyloxy-1,1'-binaphthyl-2 ', 2-diyloxycarbonyliminoethane-2,1-diyl) bisacrylate, hexane-1,6-diylbis (carbamoyloxy-1,1'- binaphthyl-2 ', 2-diyloxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (2,2,4-trimethylhexane-1,6-diyl) bis (carbamoyloxy-1,1'-binaphthyl-2' , 2-diyloxycarbonyliminoethane-2,1-diyl) bisacrylate, (2,2,4-trimethylhexane-1,6-diyl) bis (carbamoyloxy-1,1'-binaphthyl-2 ', 2-diyloxycarbonyliminoethane-2, 1-diyl) -bis (2-methylacrylate), 2 - ({[(2 '- {[(3 - {[({[2' - ({[2- (acryloyloxy) ethyl] carbamoyl} oxy) -1 , 1'-binaphthyl-2-yl] oxy} carbonyl) amino] methyl} -3,5,5-trimethylcyclohexyl) carbamoyl] oxy} -1,1'-binaphthyl-2-yl) oxy] carbonyl} amino) ethyl acrylate, 2 - ({[(2 '- {[(3 - {[({[2' - ({[2- (methacryloyloxy) ethyl] carbamoyl} oxy) -1,1'-binaphthyl-2 -yl] oxy} carbonyl) amino] methyl} -3,5,5-trimethylcyclohexyl) carbamoyl] oxy} -1,1'-binaphthyl-2-yl) oxy] carbonyl} amino) ethyl methacrylate), (6 Fluoro-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis-acrylate, (6-fluoro-1,1'- binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6-chloro-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (6-chloro-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6-bromo-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (6 -Brom-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6-iodo-1,1'-binaphthyl-2,2 ' -diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (6-iodo-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate) , (6-cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (6-cyano-1,1'-binaphthyl-2,2'-diyl ) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6-fluoro-6'-cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1- diyl) bisacrylate, (6-fluoro-6'-cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6-chloro) 6'-cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (6-chloro-6'-cyano-1, 1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6-bromo-6'-cyano-1,1'-binaphthyl-2,2 ' -diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (6-bromo-6'-cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate), (6-iodo-6'-cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bisacrylate, (6-iodo-6 ') cyano-1,1'-binaphthyl-2,2'-diyl) bis (oxycarbonyliminoethane-2,1-diyl) bis (2-methylacrylate).
Ein weiterer Gegenstand der Erfindung ist eine Photopolymer-Formulierung umfassend Matrixpolymere, Schreibmonomere und Photoinitiatoren, wobei die Schreibmonomer eine erfindungsgemäße Verbindung gemäß Formel (I) umfassen.A further subject of the invention is a photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, the writing monomers comprising a compound of the formula (I) according to the invention.
Die Matrixpolymere der erfindungsgemäßen Photopolymer-Formulierung können insbesondere vernetzt und besonders bevorzugt dreidimensional vernetzt sein.The matrix polymers of the photopolymer formulation according to the invention can in particular be crosslinked and particularly preferably crosslinked three-dimensionally.
Vorteilhaft ist auch, wenn die Matrixpolymere Polyurethane sind, wobei die die Polyurethane insbesondere durch Umsetzung wenigstens einer Polyisocyanat-Komponente a) mit wenigstens einer Isocyanat-reaktiven-Komponente b) erhältlich sein können.It is also advantageous if the matrix polymers are polyurethanes, where the polyurethanes can be obtained in particular by reacting at least one polyisocyanate component a) with at least one isocyanate-reactive component b).
Die Polyisocyanat-Komponente a) umfasst bevorzugt wenigstens eine organische Verbindung mit wenigstens zwei NCO-Gruppen. Bei diesen organischen Verbindungen kann es sich insbesondere um monomere Di- und Triisocyanate, Polyisocyanate und / oder NCOfunktionelle Prepolymere handeln. Die Polyisocyanat-Komponente a) kann auch Mischungen monomerer Di- und Triisocyanate, Polyisocyanate und / oder NCO-funktioneller Prepolymere enthalten oder daraus bestehen.The polyisocyanate component a) preferably comprises at least one organic compound having at least two NCO groups. These organic compounds may in particular be monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers. The polyisocyanate component a) may also contain or consist of mixtures of monomeric di- and triisocyanates, polyisocyanates and / or NCO-functional prepolymers.
Als monomere Di- und Triisocyanate können alle dem Fachmann an sich gut bekannten Verbindungen oder deren Mischungen eingesetzt werden. Diese Verbindungen können aromatische, araliphatische, aliphatische oder cycloaliphatische Strukturen aufweisen. In untergeordneten Mengen können die monomeren Di- und Triisocyanate auch Monoisocyanate, d.h. organische Verbindungen mit einer NCO-Gruppe umfassen.As monomeric di- and triisocyanates, it is possible to use all the compounds or mixtures thereof which are well known to the person skilled in the art. These compounds may have aromatic, araliphatic, aliphatic or cycloaliphatic structures. In subordinate In amounts, the monomeric di- and triisocyanates may also comprise monoisocyanates, ie organic compounds having an NCO group.
Beispiele für geeignete monomere Di- und Triisocyanate sind 1,4-Butandiisocyanat, 1,5-Pentandiisocyanat, 1,6-Hexandiisocyanat (Hexamethylendiisocyanat, HDI), 2,2,4-Trimethylhexamethylendiisocyanat und / oder 2,4,4-Trimethylhexamethylendiisocyanat (TMDI), Isophorondiisocyanat (IPDI), 1,8-Diisocyanato-4-(isocyanatomethyl)-octan, Bis-(4,4'-isocyanatocyclohexyl)methan und / oder Bis-(2',4-isocyanatocyclohexyl)methan und / oder deren Mischungen beliebigen Isomerengehalts, 1,4-Cyclohexandiisocyanat, die isomeren Bis-(isocyanatomethyl)cyclohexane, 2,4- und / oder 2,6-Diisocyanato-1-methylcyclohexan (Hexahydro-2,4- und / oder 2,6-toluylendiisocyanat, H6-TDI), 1,4-Phenylendiisocyanat, 2,4- und / oder 2,6-Toluylendiisocyanat (TDI), 1,5-Naphthylendiisocyanat (NDI), 2,4'- und / oder 4,4'-Diphenylmethandiisocyanat (MDI), 1,3-Bis(isocyanatomethyl)-benzol (XDI) und / oder das analoge 1,4-Isomere oder beliebige Mischungen der vorgenannten Verbindungen.Examples of suitable monomeric di- and triisocyanates are 1,4-butane diisocyanate, 1,5-pentane diisocyanate, 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI), 2,2,4-trimethylhexamethylene diisocyanate and / or 2,4,4-trimethylhexamethylene diisocyanate ( TMDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, bis (4,4'-isocyanatocyclohexyl) methane and / or bis (2 ', 4-isocyanatocyclohexyl) methane and / or their mixtures any desired isomer content, 1,4-cyclohexane diisocyanate, the isomeric bis (isocyanatomethyl) cyclohexanes, 2,4- and / or 2,6-diisocyanato-1-methylcyclohexane (hexahydro-2,4- and / or 2,6- toluene diisocyanate, H 6 -TDI), 1,4-phenylene diisocyanate, 2,4- and / or 2,6-toluene diisocyanate (TDI), 1,5-naphthylene diisocyanate (NDI), 2,4'- and / or 4,4 'Diphenylmethane diisocyanate (MDI), 1,3-bis (isocyanatomethyl) benzene (XDI) and / or the analogous 1,4-isomer or any mixtures of the aforementioned compounds.
Geeignete Polyisocyanate sind Verbindungen mit Urethan-, Harnstoff-, Carbodiimid-, Acylharnstoff-, Amid-, Isocyanurat-, Allophanat-, Biuret-, Oxadiazintrion-, Uretdion- und/oder Iminooxadiazindionstrukturen, die aus den vorgenannten Di- oder Triisocyanaten erhältlich sind.Suitable polyisocyanates are compounds having urethane, urea, carbodiimide, acylurea, amide, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and / or iminooxadiazinedione structures which are obtainable from the abovementioned di- or triisocyanates.
Besonders bevorzugt handelt es sich bei den Polyisocyanaten um oligomerisierte aliphatische und / oder cycloaliphatische Di- oder Triisocyanate, wobei insbesondere die oben stehenden aliphatischen und / oder cycloaliphatischen Di- oder Triisocyanate verwendet werden können.The polyisocyanates are particularly preferably oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates, it being possible in particular to use the abovementioned aliphatic and / or cycloaliphatic di- or triisocyanates.
Ganz besonders bevorzugt sind Polyisocyanate mit Isocyanurat-, Uretdion- und / oder Iminooxadiazindion-Strukturen sowie Biurete basierend auf HDI oder deren Mischungen.Very particular preference is given to polyisocyanates containing isocyanurate, uretdione and / or iminooxadiazinedione structures and biurets based on HDI or mixtures thereof.
Geeignete Prepolymere enthalten Urethan- und / oder Harnstoff-Gruppen sowie gegebenenfalls weitere durch Modifizierung von NCO-Gruppen entstandene Strukturen wie oben genannt. Derartige Prepolymere sind beispielsweise durch Umsetzung der oben genannten monomeren Di- und Triisocyanate und / oder Polyisocyanaten a1) mit isocyanatreaktiven Verbindungen b1) erhältlich.Suitable prepolymers contain urethane and / or urea groups and optionally further structures formed by modification of NCO groups as mentioned above. Such prepolymers are obtainable, for example, by reacting the abovementioned monomeric di- and triisocyanates and / or polyisocyanates a1) with isocyanate-reactive compounds b1).
Als isocyanatreaktive Verbindungen b1) können Alkohole, Amino oder MercaptoVerbindungen, bevorzugt Alkohole, verwendet werden. Dabei kann es sich insbesondere um Polyole handeln. Ganz besonders bevorzugt können als isocyanatreaktive Verbindung b1) Polyester-, Polyether-, Polycarbonat-, Poly(meth)acrylat- und/oder Polyurethan-Polyole verwendet werden.As isocyanate-reactive compounds b1) it is possible to use alcohols, amino or mercapto compounds, preferably alcohols. These may in particular be polyols. With very particular preference as isocyanate-reactive compound b1) Polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols can be used.
Als Polyesterpolyole sind beispielsweise lineare Polyesterdiole oder verzweigte Polyesterpolyole geeignet, die in bekannter Weise durch Umsetzung von aliphatischen, cycloaliphatischen oder aromatischen Di- bzw. Polycarbonsäuren bzw. ihren Anhydriden mit mehrwertigen Alkoholen einer OH-Funktionalität ≥ 2 erhalten werden können. Beispiele für geeignete Di- bzw. Polycarbonsäuren sind mehrwertige Carbonsäuren wie Bernstein-, Adipin-, Kork-, Sebacin-, Decandicarbon-, Phthal-, Terephthal-, Isophthal- Tetrahydrophthal- oder Trimellithsäure sowie Säureanhydride wie Phthal-, Trimellith- oder Bernsteinsäureanhydrid oder deren beliebige Gemische untereinander. Die Polyesterpolyole können auch auf natürlichen Rohstoffen wie Rizinusöl basieren. Es ist ebenfalls möglich, dass die Polyesterpolyole auf Homo- oder Mischpolymerisaten von Lactonen basieren, die bevorzugt durch Anlagerung von Lactonen bzw. Lactongemischen wie Butyrolacton, ε-Caprolacton und / oder Methyl-ε-caprolacton an hydroxyfunktionelle Verbindungen wie mehrwertige Alkohole einer OH-Funktionalität ≥ 2 beispielsweise der nachstehend genannten Art erhalten werden können.Suitable polyester polyols are, for example, linear polyester diols or branched polyester polyols which can be obtained in a known manner by reacting aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality ≥ 2. Examples of suitable di- or polycarboxylic acids are polybasic carboxylic acids such as succinic, adipic, cork, sebacic, decanedicarboxylic, phthalic, terephthalic, isophthalic, tetrahydrophthalic or trimellitic acid, as well as acid anhydrides such as phthalic, trimellitic or succinic anhydride or their arbitrary mixtures among themselves. The polyester polyols can also be based on natural raw materials such as castor oil. It is likewise possible for the polyesterpolyols to be based on homopolymers or copolymers of lactones, which preferably by addition of lactones or lactone mixtures such as butyrolactone, ε-caprolactone and / or methyl-ε-caprolactone to hydroxy-functional compounds such as polyhydric alcohols of an OH functionality ≥ 2, for example, of the type mentioned below can be obtained.
Beispiele für geeignete Alkohole sind alle mehrwertigen Alkohole wie z.B. die C2- C12-Diole, die isomeren Cyclohexandiole, Glycerin oder deren beliebige Gemische untereinander.Examples of suitable alcohols are all polyhydric alcohols such as the C 2 - C 12 diols, the isomeric cyclohexanediols, glycerol or any mixtures thereof.
Geeignete Polycarbonatpolyole sind in an sich bekannter Weise durch Umsetzung von organischen Carbonaten oder Phosgen mit Diolen oder Diol-Mischungen zugänglich.Suitable polycarbonate polyols are obtainable in a manner known per se by reacting organic carbonates or phosgene with diols or diol mixtures.
Geeignete organische Carbonate sind Dimethyl-, Diethyl- und Diphenylcarbonat.Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.
Geeignete Diole bzw. Mischungen umfassen die an sich im Rahmen der Polyestersegmente genannten mehrwertigen Alkohole einer OH-Funktionalität ≥ 2, bevorzugt Butandiol-1,4, Hexandiol-1,6 und / oder 3-Methylpentandiol. Auch Polyesterpolyole können zu Polycarbonatpolyolen umgearbeitet werden.Suitable diols or mixtures include the polyhydric alcohols of an OH functionality ≥ 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpentanediol, which are per se in the context of the polyester segments. Polyester polyols can also be converted to polycarbonate polyols.
Geeignete Polyetherpolyole sind gegebenenfalls blockweise aufgebaute Polyadditionsprodukte cyclischer Ether an OH- oder NH-funktionelle Startermoleküle.Suitable polyether polyols are optionally block-formed polyaddition of cyclic ethers to OH or NH-functional starter molecules.
Geeignete cyclische Ether sind beispielsweise Styroloxide, Ethylenoxid, Propylenoxid, Tetrahydrofuran, Butylenoxid, Epichlorhydrin sowie ihre beliebigen Mischungen.Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin and any desired mixtures thereof.
Als Starter können die an sich im Rahmen der Polyesterpolyole genannten mehrwertigen Alkohole einer OH-Funktionalität ≥ 2 sowie primäre oder sekundäre Amine und Aminoalkohole verwendet werden.The starter used may be the polyhydric alcohols having an OH functionality ≥ 2 and primary or secondary amines and amino alcohols, which are known per se within the scope of the polyester polyols.
Bevorzugte Polyetherpolyole sind solche der vorgenannten Art ausschließlich basierend auf Propylenoxid oder statistische oder Block-Copolymere basierend auf Propylenoxid mit weiteren 1-Alkylenoxiden. Besonders bevorzugt sind Propylenoxid-homopolymere sowie statistische oder Block-Copolymere, die Oxyethylen-, Oxypropylen- und / oder Oxybutyleneinheiten aufweisen, wobei der Anteil der Oxypropyleneinheiten bezogen auf die Gesamtmenge aller Oxyethylen-, Oxypropylen- und Oxybutyleneinheiten mindestens 20 Gew.-%, bevorzugt mindestens 45 Gew.-% ausmacht. Oxypropylen- und Oxybutylen umfasst hierbei alle jeweiligen linearen und verzweigten C3- und C4-Isomere.Preferred polyether polyols are those of the aforementioned type based solely on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides. Particular preference is given to propylene oxide homopolymers and also random or block copolymers which contain oxyethylene, oxypropylene and / or oxybutylene units, the proportion of oxypropylene units, based on the total amount of all oxyethylene, oxypropylene and oxybutylene units, being at least 20% by weight at least 45% by weight. Oxypropylene and oxybutylene here include all respective linear and branched C 3 and C 4 isomers.
Daneben sind als Bestandteile der Polyol-Komponente b1) als polyfunktionelle, isocyanatreaktive Verbindungen auch niedermolekulare, d.h. mit Molekulargewichten ≤ 500 g/mol, kurzkettige, d.h. 2 bis 20 Kohlenstoffatome enthaltende aliphatische, araliphatische oder cycloaliphatische di-, tri- oder polyfunktionelle Alkohole geeignet.In addition, as components of the polyol component b1) as polyfunctional, isocyanate-reactive compounds and low molecular weight, i. with molecular weights ≤ 500 g / mol, short chain, i. 2 to 20 carbon atoms containing aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols suitable.
Dies können beispielsweise in Ergänzung zu den oben genannten Verbindungen Neopentylglykol, 2-Ethyl-2-butylpropandiol, Trimethylpentandiol, stellungs-isomere Diethyloctandiole, Cyclohexandiol, 1,4-Cyclohexandimethanol, 1,6-Hexandiol, 1,2- und 1,4-Cyclohexandiol, hydriertes Bisphenol A, 2,2-Bis(4-hydroxy-cyclohexyl)-propan oder 2,2-Dimethyl-3-hydroxypropionsäure, 2,2-dimethyl-3-hydroxypropyl-ester sein. Beispiele geeigneter Triole sind Trimethylolethan, Trimethylolpropan oder Glycerin. Geeignete höherfunktionelle Alkohole sind Di-(trimethylolpropan), Pentaerythrit, Dipenta-erythrit oder Sorbit.These may include, for example, in addition to the above-mentioned compounds, neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, positional isomeric diethyloctanediols, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1,4- Cyclohexanediol, hydrogenated bisphenol A, 2,2-bis (4-hydroxy-cyclohexyl) -propane or 2,2-dimethyl-3-hydroxypropionic acid, 2,2-dimethyl-3-hydroxypropyl ester. Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerol. Suitable higher-functionality alcohols are di (trimethylolpropane), pentaerythritol, dipentaerythritol or sorbitol.
Besonders bevorzugt ist, wenn die Polyolkomponente ein difunktioneller Polyether-, Polyester oder ein Polyether-polyester-block-copolyester oder ein Polyether-Polyester-Blockcopolymer mit primären OH-Funktionen ist.It is particularly preferred if the polyol component is a difunctional polyether, polyester or a polyether-polyester block copolyester or a polyether-polyester block copolymer having primary OH functions.
Es ist ebenfalls möglich, als isocyanatreaktive Verbindungen b1) Amine einzusetzen. Beispiele geeigneter Amine sind Ethylendiamin, Propylendiamin, Diaminocyclohexan, 4,4'-Dicylohexylmethandiamin, Isophorondiamin (IPDA), difunktionelle Polyamine wie z.B. die Jeffamine®, aminterminierte Polymere, insbesondere mit zahlenmittleren Molmassen ≤ 10000 g/Mol. Mischungen der vorgenannten Amine können ebenfalls verwendet werden.It is also possible to use amines as isocyanate-reactive compounds b1). Examples of suitable amines are ethylenediamine, propylenediamine, diaminocyclohexane, 4,4'-dicyclohexylmethanediamine, isophoronediamine (IPDA), difunctional polyamines, e.g. the Jeffamine®, amine-terminated polymers, in particular having number average molecular weights ≤ 10000 g / mol. Mixtures of the aforementioned amines can also be used.
Es ist ebenfalls möglich, als isocyanatreaktive Verbindungen b1) Aminoalkohole einzusetzen. Beispiele geeigneter Aminoalkohole sind die isomeren Aminoethanole, die isomere Aminopropanole die isomeren Aminobutanole und die isomeren Aminohexanole oder deren beliebige Mischungen.It is likewise possible to use amino alcohols as isocyanate-reactive compounds b1). Examples of suitable amino alcohols are the isomeric aminoethanols, the isomeric aminopropanols the isomeric aminobutanols and the isomeric aminohexanols or any mixtures thereof.
Alle vorgenannten isocyanatreaktiven Verbindungen b1) können untereinander beliebig vermischt werden.All of the aforementioned isocyanate-reactive compounds b1) can be mixed with one another as desired.
Bevorzugt ist auch, wenn die isocyanatreaktiven Verbindungen b1) eine zahlenmittlere Molmasse von ≥ 200 und ≤ 10000 g/Mol, weiter bevorzugt ≥ 500 und ≤ 8000 g/Mol und ganz besonders bevorzugt ≥ 800 und ≤ 5000 g/Mol aufweisen. Die OH-Funktionalität der Polyole beträgt bevorzugt 1.5 bis 6.0, besonders bevorzugt 1.8 bis 4.0.It is also preferred if the isocyanate-reactive compounds b1) have a number-average molecular weight of ≥ 200 and ≦ 10000 g / mol, more preferably ≥ 500 and ≦ 8000 g / mol and very particularly preferably ≥ 800 and ≦ 5000 g / mol. The OH functionality of the polyols is preferably 1.5 to 6.0, particularly preferably 1.8 to 4.0.
Die Prepolymere der Polyisocyanat-Komponente a) können insbesondere einen Restgehalt an freiem monomeren Di- und Triisocyanaten < 1Gew.-%, besonders bevorzugt < 0.5 Gew.-% und ganz besonders bevorzugt < 0.3 Gew.-% aufweisen.The prepolymers of the polyisocyanate component a) may in particular have a residual content of free monomeric diisocyanates and triisocyanates <1% by weight, particularly preferably <0.5% by weight and very particularly preferably <0.3% by weight.
Es ist gegebenenfalls auch möglich, dass die Polyisocyanat-Komponente a) vollständig oder anteilsmäßig organische Verbindung enthält, deren NCO-Gruppen ganz oder teilweise mit aus der Beschichtungstechnologie bekannten Blockierungsmitteln umgesetzt sind. Beispiel für Blockierungsmittel sind Alkohole, Lactame, Oxime, Malonester, Pyrazole sowie Amine, wie z.B. Butanonoxim, Diisopropylamin, Malonsäurediethylester, Acetessigester, 3,5-Dimethylpyrazol, ε-Caprolactam, oder deren Mischungen.If appropriate, it is also possible for the polyisocyanate component a) to comprise completely or proportionally organic compound whose NCO groups have been completely or partially reacted with blocking agents known from coating technology. Examples of blocking agents are alcohols, lactams, oximes, malonic esters, pyrazoles and amines, such as e.g. Butanone oxime, diisopropylamine, diethyl malonate, acetoacetic ester, 3,5-dimethylpyrazole, ε-caprolactam, or mixtures thereof.
Besonders bevorzugt ist, wenn die Polyisocyanat-Komponente a) Verbindungen mit aliphatisch gebundenen NCO-Gruppen umfasst, wobei unter aliphatisch gebundenen NCO-Gruppen derartige Gruppen verstanden werden, die an ein primäres C-Atom gebunden sind. Die isocyanatreaktive Komponente b) umfasst bevorzugt wenigstens eine organische Verbindung, die im Mittel wenigstens 1.5 und bevorzugt 2 bis 3 isocyanatreaktive Gruppen aufweist. Im Rahmen der vorliegenden Erfindung werden als isocyanatreaktive Gruppen bevorzugt Hydroxy-, Amino- oder Mercapto-Gruppen angesehen.It is particularly preferred if the polyisocyanate component a) comprises compounds having aliphatically bonded NCO groups, aliphatic NCO groups being understood to mean those groups which are bonded to a primary carbon atom. The isocyanate-reactive component b) preferably comprises at least one organic compound which has on average at least 1.5 and preferably from 2 to 3 isocyanate-reactive groups. In the context of the present invention, hydroxy, amino or mercapto groups are preferably considered as isocyanate-reactive groups.
Die isocyanatreaktive Komponente kann insbesondere Verbindungen umfassen, die im Zahlenmittel wenigstens 1.5 und bevorzugt 2 bis 3 isocyanatreaktive Gruppen aufweisen.The isocyanate-reactive component may in particular comprise compounds which have a number average of at least 1.5 and preferably 2 to 3 isocyanate-reactive groups.
Geeignete polyfunktionelle, isocyanatreaktive Verbindungen der Komponente b) sind beispielsweise die oben beschriebenen Verbindungen b1).Suitable polyfunctional, isocyanate-reactive compounds of component b) are, for example, the compounds b1) described above.
Bei einer weiteren bevorzugten Ausführungsform ist vorgesehen, dass die Schreibmonomere ein mono- und / oder ein multifunktionelles (Meth)acrylat-Schreibmonomere umfassen. Ganz besonders bevorzugt können die Schreibmonomere zusätzlich wenigstens ein mono- und / oder ein multifunktionelles Urethan(meth)acrylat umfassen.In a further preferred embodiment it is provided that the writing monomers comprise a mono- and / or a multifunctional (meth) acrylate writing monomer. Most preferably, the random monomers may additionally comprise at least one mono- and / or one multifunctional urethane (meth) acrylate.
Geeignete Acrylat-Schreibmonomere sind insbesondere Verbindungen der allgemeinen Formel (II)
Als Acrylate bzw. Methacrylate werden vorliegend Ester der Acrylsäure bzw. Methacrylsäure bezeichnet. Beispiele bevorzugt verwendbarer Acrylate und Methacrylate sind Phenylacrylat, Phenylmethacrylat, Phenoxyethylacrylat, Phenoxyethylmethacrylat, Phenoxyethoxyethylacrylat, Phenoxyethoxyethylmethacrylat, Phenylthioethylacrylat, Phenylthioethylmethacrylat, 2-Naphthylacrylat, 2-Naphthylmethacrylat, 1,4-Bis-(2-thionaphthyl)-2-butylacrylat, 1,4-Bis-(2-thionaphthyl)-2-butylmethacrylat, Bisphenol A Diacrylat, Bisphenol A Dimethacrylat, sowie deren ethoxylierte Analogverbindungen, N-Carbazolylacrylate.As acrylates or methacrylates herein esters of acrylic acid or methacrylic acid are referred to. Examples of preferably usable acrylates and methacrylates are phenyl acrylate, phenyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl acrylate, phenoxyethoxyethyl methacrylate, phenylthioethyl acrylate, phenylthioethyl methacrylate, 2-naphthyl acrylate, 2-naphthyl methacrylate, 1,4-bis (2-thionaphthyl) -2-butyl acrylate, 1.4 Bis (2-thionaphthyl) -2-butyl methacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, and their ethoxylated analogues, N-carbazolyl acrylates.
Als Urethanacrylate werden vorliegend Verbindungen mit mindestens einer Acrylsäureestergruppe und mindestens eine Urethanbindung verstanden. Solche Verbindungen können beispielsweise durch Umsetzung eines Hydroxy-funktionellen Acrylats oder Methacrylats mit einer Isocyanat-funktionellen Verbindung erhalten werden.Urethane acrylates in the present context are understood as meaning compounds having at least one acrylic acid ester group and at least one urethane bond. Such compounds can be obtained, for example, by reacting a hydroxy-functional acrylate or methacrylate with an isocyanate-functional compound.
Beispiele hierfür verwendbarer Isocyanat-funktionelle Verbindungen sind Monoisocyanate sowie die unter a) genannten monomeren Diisocyanate, Triisocyanate und / oder Polyisocyanate. Beispiele geeigneter Monoisocyanate sind Phenylisocyanat, die isomeren Methylthiophenylisocyanate. Di-, Tri- oder Polyisocyanate sind oben genannt sowie Triphenylmethan-4,4',4"-triisocyanat und Tris(p-isocyanatophenyl)thiophosphat oder deren Derivate mit Urethan-, Harnstoff-, Carbodiimid-, Acylharnstoff-, Isocyanurat-, Allophanat-, Biuret-, Oxadiazintrion-, Uretdion-, Iminooxadiazindionstruktur und Mischungen derselben. Bevorzugt sind dabei aromatische Di-, Tri- oder Polyisocyanate.Examples of suitable isocyanate-functional compounds are monoisocyanates and the monomeric diisocyanates, triisocyanates and / or polyisocyanates mentioned under a). Examples of suitable monoisocyanates are phenyl isocyanate, the isomeric Methylthiophenylisocyanate. Di-, tri- or polyisocyanates are mentioned above as well as triphenylmethane-4,4 ', 4 "-triisocyanate and tris (p-isocyanatophenyl) thiophosphate or their derivatives with urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate , Biuret, oxadiazinetrione, uretdione, iminooxadiazinedione and mixtures thereof. Preferred are aromatic di-, tri- or polyisocyanates.
Als hydroxyfunktionelle Acrylate oder Methacrylate für die Herstellung von Urethanacrylaten kommen beispielsweise Verbindungen wie 2-Hydroxyethyl(meth)acrylat, Polyethylenoxid-mono(meth)acrylate, Polypropylenoxidmono(meth)acrylate, Polyalkylenoxidmono(meth)-acrylate, Poly(ε-caprolacton)mono(meth)acrylate, wie z.B. Tone® M100 (Dow, Schwalbach, DE), 2-Hydroxypropyl(meth)acrylat, 4-Hydroxybutyl(meth)acrylat, 3-Hydroxy-2,2-dimethylpropyl-(meth)acrylat, Hydroxypropyl(meth)acrylat, Acrylsäure-(2-hydroxy-3-phenoxypropylester), die hydroxyfunktionellen Mono-, Di- oder Tetraacrylate mehrwertiger Alkohole wie Trimethylolpropan, Glycerin, Pentaerythrit, Dipentaerythrit, ethoxyliertes, propoxyliertes oder alkoxyliertes Trimethylolpropan, Glycerin, Pentaerythrit, Dipentaerythrit oder deren technische Gemische. Bevorzugt sind 2-Hydroxyethylacrylat, Hydroxypropylacrylat, 4-Hydroxybutylacrylat und Poly(ε-caprolacton)mono(meth)acrylat.Suitable hydroxy-functional acrylates or methacrylates for the preparation of urethane acrylates are, for example, compounds such as 2-hydroxyethyl (meth) acrylate, polyethylene oxide mono (meth) acrylates, polypropylene oxide mono (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly (ε-caprolactone) mono (meth) acrylates, such as Tone® M100 (Dow, Schwalbach, DE), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxypropyl (meth) acrylate, acrylic acid (2-hydroxy-3-phenoxypropyl ester), the hydroxy-functional mono-, di- or tetraacrylates of polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or technical mixtures thereof. Preference is given to 2-hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate and poly (ε-caprolactone) mono (meth) acrylate.
Ebenfalls verwendet werden können die an sich bekannten hydroxylgruppenhaltigen Epoxy(meth)acrylate mit OH-Gehalten von 20 bis 300 mg KOH/g oder hydroxylgruppenhaltige Polyurethan(meth)acrylate mit OH-Gehalten von 20 bis 300 mg KOH/g oder acrylierte Polyacrylate mit OH-Gehalten von 20 bis 300 mg KOH/g sowie deren Mischungen untereinander und Mischungen mit hydroxylgruppenhaltigen ungesättigten Polyestern sowie Mischungen mit Polyester(meth)acrylaten oder Mischungen hydroxylgruppenhaltiger ungesättigter Polyester mit Polyester(meth)acrylaten.It is also possible to use the hydroxyl-containing epoxy (meth) acrylates known per se with OH contents of 20 to 300 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates with OH contents of 20 to 300 mg KOH / g or acrylated polyacrylates with OH Contents of 20 to 300 mg KOH / g and mixtures thereof and mixtures with hydroxyl-containing unsaturated polyesters and mixtures with polyester (meth) acrylates or mixtures of hydroxyl-containing unsaturated polyester with polyester (meth) acrylates.
Bevorzugt sind insbesondere Urethanacrylate erhältlich aus der Umsetzung von Tris(p-isocyanatophenyl)thiophosphat und / oder m-Methylthiophenylisocyanat mit alkoholfunktionellen Acrylaten wie Hydroxyethyl(meth)acrylat, Hydroxypropyl(meth)acrylat und / oder Hydroxybutyl(meth)acrylat.In particular, urethane acrylates are obtainable from the reaction of tris (p-isocyanatophenyl) thiophosphate and / or m-methylthiophenyl isocyanate with alcohol-functional acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and / or hydroxybutyl (meth) acrylate.
Ebenso ist es möglich, dass das Schreibmonomer weitere ungesättigte Verbindungen wie α,β-ungesättigte Carbonsäurederivate wie beispielsweise Maleinate, Fumarate, Maleimide, Acrylamide, weiterhin Vinylether, Propenylether, Allylether und Dicyclopentadienyl-Einheiten enthaltende Verbindungen sowie olefinisch ungesättigte Verbindungen wie z.B. Styrol, α-Methylstyrol, Vinyltoluol und / oder Olefine, umfasst.It is also possible that the writing monomer further unsaturated compounds such as α, β-unsaturated carboxylic acid derivatives such as maleinates, fumarates, maleimides, acrylamides, vinyl ethers, propenyl ethers, allyl ether and dicyclopentadienyl units containing compounds and olefinically unsaturated compounds such. Styrene, α-methylstyrene, vinyltoluene and / or olefins.
Erfindungsgemäß geeignete Photoinitiatoren sind üblicherweise durch aktinische Strahlung aktivierbare Verbindungen, die eine Polymerisation der Schreibmonomere auslösen können. Bei den Photoinitiatoren kann zwischen unimolekularen (Typ I) und bimolekularen (Typ II) Initiatoren unterschieden werden. Des Weiteren werden sie je nach ihrer chemischen Natur in Photoinitiatoren für radikalische, anionische, kationische oder gemischte Art der Polymerisation unterschieden.Photoinitiators which are suitable according to the invention are usually compounds which can be activated by actinic radiation and which can initiate a polymerization of the writing monomers. In the photoinitiators, a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators. Furthermore, depending on their chemical nature, they are distinguished in photoinitiators for radical, anionic, cationic or mixed type of polymerization.
Typ I-Photoinitiatoren (Norrish-Typ-I) für die radikalische Photopolymerisation bilden beim Bestrahlen durch eine unimolekulare Bindungsspaltung freie Radikale. Beispiele für Typ I-Photoinitiatoren sind Triazine, Oxime, Benzoinether, Benzilketale, Bis-imidazole, Aroylphosphinoxide, Sulfonium- und Iodoniumsalze.Type I photoinitiators (Norrish type I) for radical photopolymerization form free radicals upon irradiation by unimolecular bond cleavage. Examples of type I photoinitiators are triazines, oximes, benzoin ethers, benzil ketals, bisimidazoles, aroylphosphine oxides, sulfonium and iodonium salts.
Typ II-Photoinitiatoren (Norrish-Typ-II) für die radikalische Polymerisation bestehen aus einem Farbstoff als Sensibilisator und einem Coinitiator und durchlaufen bei der Bestrahlung mit auf den Farbstoff angepasstem Licht eine bimolekulare Reaktion. Zunächst absorbiert der Farbstoff ein Photon und überträgt aus einem angeregten Zustand Energie auf den Coinitiator. Dieser setzt durch Elektronen- oder Protonentransfer oder direkte Wasserstoffabstraktion die polymerisationsauslösenden Radikale frei.Radical polymerization type II photoinitiators (Norrish type II) consist of a dye as a sensitizer and a coinitiator and undergo a bimolecular reaction upon irradiation with dye-adapted light. First, the dye absorbs a photon and transfers energy to the coinitiator from an excited state. This releases the polymerization-initiating radicals by electron or proton transfer or direct hydrogen abstraction.
Im Sinne dieser Erfindung werden bevorzugt Typ II-Photoinitiatoren verwendet.For the purposes of this invention, type II photoinitiators are preferably used.
Farbstoff und Coinitiator der Typ II-Photoinitiatoren können entweder unmittelbar gemeinsam mit den weiteren Komponenten des Photopolymers vermischt werden oder aber auch jeweils mit Einzelkomponenten vorvermischt werden. Insbesondere wenn das Photopolymer Polyurethan-Matrixpolymere enthalten soll, kann der Farbstoff mit der Isocyanat-reaktiven Komponente und der Coinitiator mit der Isocyanat-Komponente vorvermischt werden. Ebenso ist es aber auch möglich den Coinitiator mit der Isocyanat-reaktiven Komponente und den Farbstoff mit der Isocyanat-Komponente vorzuvermischen.Dye and coinitiator of the type II photoinitiators can either be mixed directly together with the other components of the photopolymer or else premixed with individual components. In particular, when the photopolymer is to contain polyurethane matrix polymers, the dye having the isocyanate-reactive component and the coinitiator may be premixed with the isocyanate component. However, it is also possible to pre-mix the coinitiator with the isocyanate-reactive component and the dye with the isocyanate component.
Solche Photoinitiatorsysteme sind prinzipiell in der
Geeignete Farbstoffe, die zusammen mit einem Ammoniumalkylarylborat einen Typ II-Photoinitiator bilden, sind die in der
Unter kationischen Farbstoffen werden bevorzugt solche der folgenden Klassen verstanden: Acridin-Farbstoffe, Xanthen-Farbstoffe, Thioxanthen-Farbstoffe, Phenazin-Farbstoffe, Phenoxazin-Farbstoffe, Phenothiazin-Farbstoffe, Tri(het)arylmethan-Farbstoffe - insbesondere Diamino- und Triamino(het)arylmethan-Farbstoffe, Mono-, Di-, Tri- und Pentamethincyanin-Farbstoffe, Hemicyanin-Farbstoffe, extern kationische Merocyanin-Farbstoffe, extern kationische Neutrocyanin-Farbstoffe, Nullmethin-Farbstoffe - insbesondere Naphtholactam-Farbstoffe, Streptocyanin-Farbstoffe. Solche Farbstoffe sind beispielsweise in
Besonders bevorzugt sind Phenazin-Farbstoffe, Phenoxazin-Farbstoffe, Phenothiazin-Farbstoffe, Tri(het)arylmethan-Farbstoffe - insbesondere Diamino- und Triamino(het)arylmethan-Farbstoffe, Mono-, Di-, Tri- und Pentamethincyanin-Farbstoffe, Hemicyanin-Farbstoffe, Nullmethin-Farbstoffe - insbesondere Naphtholactam-Farbstoffe, Streptocyanin-Farbstoffe.Particularly preferred are phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri (het) arylmethane dyes - especially diamino and triamino (het) arylmethane dyes, mono-, di-, tri- and pentamethine cyanine dyes, hemicyanine Dyes, zero methine dyes - especially naphtholactam dyes, streptocyanine dyes.
Beispiele für kationische Farbstoffe sind Astrazon Orange G, Basic Blue 3, Basic Orange 22, Basic Red 13, Basic Violett 7, Methylenblau, Neu Methylenblau, Azur A, 2,4-Diphenyl-6-(4-methoxyphenyl)pyrylium, Safranin O, Astraphloxin, Brilliant Grün, Kristallviolett, Ethylviolett und Thionin.Examples of cationic dyes are Astrazon Orange G,
Bevorzugte Anionen sind insbesondere C8- bis C25-Alkansulfonat, vorzugsweise C13- bis C25-Alkansulfonat, C3- bis C18-Perfluoralkansulfonat, C4- bis C18-Perfluoralkansulfonat, das in der Alkylkette mindestens 3 Wasserstoffatome trägt, C9- bis C25-Alkanoat, C9- bis C25-Alkenoat, C8- bis C25-Alkylsulfat, vorzugsweise C13- bis C25-Alkylsulfat, C8- bis C25-Alkenylsulfat, vorzugsweise C13- bis C25-Alkenylsulfat, C3- bis C18-Perfluoralkylsulfat, C4-bis C18-Perfluoralkylsulfat, das in der Alkylkette mindestens 3 Wasserstoffatome trägt, Polyethersulfate basierend auf mindestens 4 Äquivalenten Ethylenoxid und/oder Äquivalenten 4 Propylenoxid, Bis-C4- bis C25-Alkyl-, C5- bis C7-Cycloalkyl-, C3- bis Cs-Alkenyl- oder C7-bis C11-Aralkyl-sulfosuccinat, durch mindestens 8 Fluoratome substituiertes Bis-C2-bis C10-alkyl-sulfosuccinat, C8- bis C25-Alkyl-sulfoacetate, durch mindestens einen Rest der Gruppe Halogen, C4- bis C25-Alkyl, Perfluor-C1- bis Cs-Alkyl und/oder C1- bis C12-Alkoxycarbonyl substituiertes Benzolsulfonat, ggf. durch Nitro, Cyano, Hydroxy, C1- bis C25-Alkyl, C1- bis C12-Alkoxy, Amino, C1- bis C12-Alkoxycarbonyl oder Chlor substituiertes Naphthalin- oder Biphenylsulfonat, ggf. durch Nitro, Cyano, Hydroxy, C1- bis C25-Alkyl, C1- bis C12-Alkoxy, C1- bis C12-Alkoxycarbonyl oder Chlor substituiertes Benzol-, Naphthalin- oder Biphenyldisulfonat, durch Dinitro, C6- bis C25-Alkyl, C4- bis C12-Alkoxycarbonyl, Benzoyl, Chlorbenzoyl oder Toluoyl substituiertes Benzoat, das Anion der Naphthalindicarbonsäure, Diphenyletherdisulfonat, sulfonierte oder sulfatierte, ggf. mindestens einfach ungesättigte C8- bis C25-Fettsäureester von aliphatischen C1- bis C8-Alkoholen oder Glycerin, Bis-(sulfo-C2- bis C6-alkyl)-C3- bis C12-alkandicarbonsäureester, Bis-(sulfo-C2- bis C6-alkyl)-itaconsäureester, (Sulfo-C2- bis C6-alkyl)-C6- bis C18-alkancarbonsäureester, (Sulfo-C2- bis C6-alkyl)-acryl- oder methacrylsäureester, ggf. durch bis zu 12 Halogenreste substituiertes Triscatecholphosphat, ein Anion der Gruppe Tetraphenylborat, Cyanotriphenylborat, Tetraphenoxyborat, C4- bis C12-Alkyl-triphenylborat, deren Phenyl- oder Phenoxy-Reste durch Halogen, C1- bis C4-Alkyl und/oder C1- bis C4-Alkoxy substituiert sein können, C4- bis C12-Alkyl-trinaphthylborat, Tetra-Ci- bis C20-alkoxyborat, 7,8- oder 7,9-Dicarba-nido-undecaborat(1-) oder (2-), die gegebenenfalls an den B- und/oder C-Atomen durch eine oder zwei C1- bis C12-Alkyl- oder Phenyl-Gruppen substituiert sind, Dodecahydro-dicarbadodecaborat(2-) oder B-C1- bis C12-Alkyl-C-phenyl-dodecahydro-dicarbadodecaborat(1-) steht, wobei bei mehrwertigen Anionen wie Naphthalindisulfonat A- für ein Äquivalent dieses Anions steht, und wobei die Alkan- und Alkylgruppen verzweigt sein können und/oder durch Halogen, Cyano, Methoxy, Ethoxy, Methoxycarbonyl oder Ethoxycarbonyl substituiert sein können.Preferred anions are in particular C 8 - to C 25 alkane, preferably C 13 - to C 25 alkane, C 3 - to C 18 -Perfluoralkansulfonat, C 4 - to C 18 -Perfluoralkansulfonat carrying at least 3 hydrogen atoms in the alkyl chain, C 9 - to C 25 -alkanoate, C 9 - to C 25 -alkenoate, C 8 - to C 25 -alkyl sulfate, preferably C 13 - to C 25 -alkyl sulfate, C 8 - to C 25 -alkenyl sulfate, preferably C 13 - to C 25 alkenyl sulfate, C 3 to C 18 perfluoroalkyl sulfate, C 4 to C 18 perfluoroalkyl sulfate bearing at least 3 hydrogen atoms in the alkyl chain, polyether sulfates based on at least 4 equivalents of ethylene oxide and / or equivalents 4 propylene oxide, bis-C 4 to C 25 alkyl, C 5 to C 7 cycloalkyl, C 3 to Cs alkenyl or C 7 to C 11 aralkyl sulfosuccinate, bis-C 2 -bis substituted by at least 8 fluorine atoms C 10 -alkyl sulfosuccinate, C 8 - to C 25 -alkyl sulfoacetates, by at least one radical of the group halogen, C 4 - to C 25 -A benzenesulfonate substituted by alkyl, perfluoro-C 1 -C 5 -alkyl and / or C 1 -C 12 -alkoxycarbonyl, optionally by nitro, cyano, hydroxy, C 1 - to C 25 -alkyl, C 1 - to C 12 - Alkoxy, amino, C 1 - to C 12 -alkoxycarbonyl or chlorine-substituted naphthalene or biphenylsulfonate, optionally by nitro, cyano, hydroxy, C 1 - to C 25 -alkyl, C 1 - to C 12 -alkoxy, C 1 - to C 12 alkoxycarbonyl or chlorine-substituted benzene, naphthalene or biphenyl disulfonate, benzoate substituted by dinitro, C 6 - to C 25 -alkyl, C 4 - to C 12 -alkoxycarbonyl, benzoyl, chlorobenzoyl or toluoyl, the anion of naphthalenedicarboxylic acid, Diphenyl ether disulfonate, sulfonated or sulfated, optionally at least monounsaturated C 8 - to C 25 -fatty acid esters of aliphatic C 1 - to C 8 -alcohols or glycerol, bis- (sulfo-C 2 - to C 6 -alkyl) -C 3 - to C 12 -alkandicarbonsäureester, bis (sulfo-C 2 - to C 6 -alkyl) -itaconsäureester, (sulfo-C 2 - to C 6 -alkyl) -C 6 - to C 18 -alkanca Rbonsäureester, (sulfo-C 2 - to C 6 -alkyl) acrylic or methacrylic acid esters, optionally substituted by up to 12 halogen radicals triscatechol phosphate, an anion of the group tetraphenylborate, cyanotriphenylborate, tetraphenoxyborate, C 4 - to C 12 -alkyl-triphenylborat , whose phenyl or phenoxy radicals by Halogen, C 1 - to C 4 -alkyl and / or C 1 - to C 4 -alkoxy, C 4 - to C 12 -alkyl-trinaphthylborate, tetra-C 1 - to C 20 -alkoxyborate, 7,8- or 7,9-dicarba-nido undecaborate (1-) or (2-) optionally substituted at the B and / or C atoms by one or two C 1 to C 12 alkyl or phenyl groups are dodecahydro-dicarbadodecaborate (2-) or BC 1 - to C 12 alkyl-C-phenyl-dodecahydro-dicarbadodecaborate (1-), wherein in polyvalent anions such as naphthalenedisulfonate A - is one equivalent of this anion, and wherein the Alkane and alkyl groups may be branched and / or may be substituted by halogen, cyano, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl.
Bevorzugt ist auch, wenn das Anion A- des Farbstoffs einen AClogP im Bereich von 1 bis 30, besonders bevorzugt im Bereich von 1 bis 12 und insbesondere bevorzugt im Bereich von 1 bis 6,5 aufweist. Der AClogP wird nach
Geeignete Ammoniumalkylarylborate sind beispielsweise (
Es kann vorteilhaft sein, Gemische dieser Photoinitiatoren einzusetzen. Je nach verwendeter Strahlungsquelle muss Typ und Konzentration an Photoinitiator in dem Fachmann bekannter Weise angepasst werden. Näheres ist zum Beispiel in
Ganz besonders bevorzugt ist, wenn der Photoinitiator eine Kombination von Farbstoffen, deren Absorptionsspektren zumindest teilweise den Spektralbereich von 400 bis 800 nm abdecken, mit wenigstens einem auf die Farbstoffe abgestimmten Coinitiator umfasst.It is very particularly preferred if the photoinitiator comprises a combination of dyes whose absorption spectra at least partially cover the spectral range from 400 to 800 nm with at least one co-initiator adapted to the dyes.
Bevorzugt ist auch, wenn wenigstens ein für eine Laserlichtfarbe ausgewählt aus blau, grün und rot geeigneter Photoinitiator in der Photopolymer-Formulierung enthalten ist.It is also preferred if at least one suitable for a laser light color of blue, green and red photoinitiator is included in the photopolymer formulation.
Weiter bevorzugt ist auch, wenn die Photopolymer-Formulierung für wenigstens zwei Laserlichtfarben ausgewählt aus blau, grün und rot je einen geeigneten Photoinitiator enthält.It is also preferred if the photopolymer formulation contains at least two laser light colors selected from blue, green and red each contain a suitable photoinitiator.
Ganz besonders bevorzugt ist schließlich, wenn die Photopolymer-Formulierung für jede der Laserlichtfarben blau, grün und rot jeweils einen geeigneten Photoinitiator enthält.Finally, it is very particularly preferred if the photopolymer formulation in each case contains a suitable photoinitiator for each of the laser light colors blue, green and red.
Gemäß einer weiteren bevorzugten Ausführungsform ist vorgesehen, dass die Photopolymer-Formulierung zusätzlich monomere Urethane als Additive enthält, wobei die Urethane insbesondere mit wenigstens einem Fluoratom substituiert sein können.According to another preferred embodiment, it is provided that the photopolymer formulation additionally contains monomeric urethanes as additives, wherein the urethanes may be substituted in particular with at least one fluorine atom.
Bevorzugt können die Urethane die allgemeine Formel (III)
Ebenfalls Gegenstand der Erfindung ist ein holografisches Medium, umfassend Matrixpolymere, Schreibmonomere und Photoinitiatoren, wobei die Schreibmonomere eine erfindungsgemäße Verbindung gemäß Formel (I) umfassen.The invention likewise provides a holographic medium comprising matrix polymers, writing monomers and photoinitiators, the writing monomers comprising a compound of the formula (I) according to the invention.
Die für die erfindungsgemäße Photopolymer-Formulierung beschriebenen, oben stehenden, weiteren bevorzugten Ausführungsformen auch bevorzugte Ausführungsformen des erfindungsgemäßen holographischen Mediums dar.The above-described further preferred embodiments described above for the photopolymer formulation according to the invention are also preferred embodiments of the holographic medium according to the invention.
Gemäß einer bevorzugten Ausführungsform des holgraphischen Mediums ist vorgesehen, dass die Matrixpolymere vernetzt, bevorzugt dreidimensional vernetzt und ganz besonders bevorzugt dreidimensional vernetzte Polyurethane sind.According to a preferred embodiment of the holgraphic medium, it is provided that the matrix polymers are crosslinked, preferably three-dimensionally crosslinked, and very particularly preferably three-dimensionally crosslinked polyurethanes.
Bevorzugt ist auch, wenn das holographische Medium wenigstens ein Fluorurethan als Additiv umfasst.It is also preferred if the holographic medium comprises at least one fluorourethane as an additive.
Das holografische Medium kann insbesondere ein Films sein, der bevorzugt eine Filmdicke von 0.5 µm bis 200 µm, weiter bevorzugt von 0.8 µm bis 50 µm und besonders bevorzugt von 1µm bis 25 µm aufweisen kann.In particular, the holographic medium may be a film which may preferably have a film thickness of from 0.5 μm to 200 μm, more preferably from 0.8 μm to 50 μm, and particularly preferably from 1 μm to 25 μm.
In das holografische Medium kann auch wenigstens ein Hologramm einbelichtet sein.At least one hologram can also be imprinted in the holographic medium.
In die erfindungsgemäßen holographischen Medien können durch entsprechende Belichtungsprozesse für optische Anwendungen im gesamten sichtbaren und nahen UV-Bereich (300-800 nm) Hologrammen einbelichtet werden. Visuelle Hologramme umfassen alle Hologramme, die nach dem Fachmann bekannten Verfahren aufgezeichnet werden können. Darunter fallen unter anderem In-Line (Gabor) Hologramme, Off-Axis Hologramme, Full-Aperture Transfer Hologramme, Weißlicht-Transmissionshologramme ("Regenbogenhologramme), Denisyukhologramme, Off-Axis Reflektionshologramme, Edge-Lit Hologramme sowie holographische Stereogramme. Bevorzugt sind Reflektionshologramme, Denisyukhologramme, Transmissionshologramme.Holograms can be imprinted into the holographic media according to the invention by appropriate exposure processes for optical applications in the entire visible and near UV range (300-800 nm). Visual holograms include all holograms that can be recorded by methods known to those skilled in the art. These include in-line (Gabor) holograms, off-axis holograms, full-aperture transfer holograms, white-light transmission holograms, denisy-holograms, off-axis reflection holograms, edge-lit holograms, and holographic stereograms. Denisyuk holograms, transmission holograms.
Mögliche optische Funktionen der Hologramme entsprechen den optische Funktionen von Lichtelementen wie Linsen, Spiegel, Umlenkspiegel, Filter, Streuscheiben, Beugungselemente, Diffusoren, Lichtleiter, Lichtlenker (waveguides), Projektionsscheiben und/oder Masken. Ebenfalls können Kombinationen aus dies optischen Funktionen unabhängig voneinander in einem Hologramm vereinigt sein. Häufig zeigen diese optischen Elemente eine Frequenzselektivität, je nachdem wie die Hologramme belichtet wurden und welche Dimensionen das Hologramm hat.Possible optical functions of the holograms correspond to the optical functions of light elements such as lenses, mirrors, deflection mirrors, filters, diffusers, diffractive elements, diffusers, light guides, waveguides, projection screens and / or masks. Also, combinations of these optical functions may be unified independently in a hologram. Frequently, these optical elements exhibit frequency selectivity depending on how the holograms were exposed and the dimensions of the hologram.
Zudem können mittels der erfindungsgemäßen Medien auch holographische Bilder oder Darstellungen hergestellt werden, wie zum Beispiel für persönliche Portraits, biometrische Darstellungen in Sicherheitsdokumenten, oder allgemein von Bilder oder Bildstrukturen für Werbung, Sicherheitslabels, Markenschutz, Markenbranding, Etiketten, Designelementen, Dekorationen, Illustrationen, Sammelkarten, Bilder und dergleichen sowie Bilder, die digitale Daten repräsentieren können u.a. auch in Kombination mit den zuvor dargestellten Produkten. Holographische Bilder können den Eindruck eines dreidimensionalen Bildes haben, sie können aber auch Bildsequenzen, kurze Filme oder eine Anzahl von verschiedenen Objekten darstellen, je nachdem aus welchem Winkel, mit welcher (auch bewegten) Lichtquelle etc. diese beleuchtet wird. Aufgrund dieser vielfältigen Design-Möglichkeiten stellen Hologramme, insbesondere Volumenhologramme, eine attraktive technische Lösung für die oben genannten Anwendung dar.In addition, holographic images or representations can also be produced by means of the media according to the invention, for example for personal portraits, biometric representations in security documents, or generally for images or image structures for advertising, security labels, trademark protection, branding, labels, design elements, decorations, illustrations, trading cards , Images and the like, as well as images that can represent digital data, including in combination with the previously presented products. Holographic images can have the impression of a three-dimensional image, but they can also represent image sequences, short films or a number of different objects, depending on which angle, with which (even moving) light source, etc., this is illuminated. Because of these diverse design possibilities, holograms, in particular volume holograms, represent an attractive technical solution for the above-mentioned application.
Weiterhin Gegenstand der vorliegenden Erfindung ist die Verwendung eines erfindungsgemäßen holographischen Mediums zur Aufzeichnung von In-Line, Off-Axis, Full-Aperture Transfer, Weißlicht-Transmissions, Denisyuk, Off-Axis Reflektions oder Edge-Lit Hologrammen sowie holographischen Stereogrammen, insbesondere zur Herstellung von optischen Elementen, Bildern oder Bilddarstellungen.The present invention furthermore relates to the use of a holographic medium according to the invention for recording in-line, off-axis, full-aperture transfer, white-light transmissions, denisyuk, off-axis reflection or edge-lit holograms and holographic stereograms, in particular for the production of optical elements, images or image representations.
Ebenfalls Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung eines holographischen Mediums unter Verwendung einer erfindungsgemäßen Photopolymer-Formulierung.Likewise provided by the present invention is a process for producing a holographic medium using a photopolymer formulation according to the invention.
Die Photopolymer-Formulierungen können insbesondere zur Herstellung holographischer Medien in Form eines Films verwendet werden. Dabei wird als Träger eine Lage eines für Licht im sichtbaren Spektralbereich (Transmission größer als 85% im Wellenlängenbereich von 400 bis 780 nm) transparenten Materials oder Materialverbunds ein- oder beidseitig beschichtet sowie ggf. eine Abdeckschicht auf der oder den Photopolymerlagen appliziert.The photopolymer formulations can be used in particular for producing holographic media in the form of a film. In this case, a layer of a material or composite material transparent to light in the visible spectral range (transmission greater than 85% in the wavelength range from 400 to 780 nm) is coated on one or both sides and optionally a cover layer applied to the photopolymer layer (s).
Bevorzugte Materialien oder Materialverbünde des Trägers basieren auf Polycarbonat (PC), Polyethylenterephthalat (PET), Polybutylenterephthalat, Polyethylen, Polypropylen, Celluloseacetat, Cellulosehydrat, Cellulosenitrat, Cycloolefinpolymere, Polystyrol, Polyepoxide, Polysulfon, Cellulosetriacetat (CTA), Polyamid, Polymethylmethacrylat, Polyvinylchlorid, Polyvinylbutyral oder Polydicyclopentadien oder deren Mischungen. Besonders bevorzugt basieren sie auf PC, PET und CTA. Materialverbünde können Folienlaminate oder Coextrudate sein. Bevorzugte Materialverbünde sind Duplex- und Triplexfolien aufgebaut nach einem der Schemata A/B, A/B/A oder A/B/C. Besonders bevorzugt sind PC/PET, PET/PC/PET und PC/TPU (TPU = Thermoplastisches Polyurethan).Preferred materials or composite materials of the carrier are based on polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene, polypropylene, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, polyepoxides, polysulfone, cellulose triacetate (CTA), polyamide, polymethyl methacrylate, polyvinyl chloride, polyvinyl butyral or polydicyclopentadiene or mixtures thereof. Most preferably, they are based on PC, PET and CTA. Composite materials may be film laminates or co-extrudates. Preferred composite materials are duplex and triplex films constructed according to one of the schemes A / B, A / B / A or A / B / C. Especially preferred are PC / PET, PET / PC / PET and PC / TPU (TPU = Thermoplastic Polyurethane).
Die Materialien oder Materialverbünde des Trägers können einseitig oder beidseitig antihaftend, antistatisch, hydrophobiert oder hydrophiliert ausgerüstet sein. Die genannten Modifikationen dienen an der Photopolymerschicht zugewandten Seite dem Zweck, dass die Photopolymerlage von dem Träger zerstörungsfrei abgelöst werden kann. Eine Modifikation der der Photopolymerlage abgewandten Seite des Trägers dient dazu, dass die erfindungsgemäßen Medien speziellen mechanischen Anforderungen genügen, die z.B. bei der Verarbeitung in Rollenlaminatoren, insbesondere bei Rolle-zu-Rolle-Verfahren, gefordert sind.The materials or composite materials of the carrier may be unilaterally or bilaterally anti-adhesive, antistatic, hydrophobed or hydrophilated. The modifications mentioned serve on the photopolymer layer side facing the purpose that the photopolymer layer can be detached from the carrier nondestructive. A modification of the side of the carrier remote from the photopolymer layer serves to ensure that the media according to the invention satisfy special mechanical requirements, e.g. when processing in roll laminators, especially in roll-to-roll processes.
Noch ein Gegenstand der Erfindung ist auch ein Display umfassend ein erfindungsgemäßes holografische Medium.Another object of the invention is also a display comprising a holographic medium according to the invention.
Beispiele für derartige Displays sind beispielsweise in der
Die vorliegende Erfindung wird im Folgenden anhand von Beispielen näher erläutert.The present invention will be explained in more detail below with reference to examples.
Die wie im Abschnitt "Herstellung der Medien zur Bestimmung der holographischen Eigenschaften" beschrieben hergestellten Medien wurden mittels einer Messanordnung gemäß
Es wurden auf folgende Weise Hologramme in das Medium geschrieben:
- Beide Shutter (S) sind für die Belichtungszeit t geöffnet.
- Danach wurde bei geschlossenen Shuttern (S)
dem Medium 5 Minuten Zeit für die Diffusion der noch nicht polymerisierten Schreibmonomere gelassen.
- Both shutters (S) are open for the exposure time t.
- Thereafter, with closed shutters (S), the medium was allowed 5 minutes for the diffusion of the unpolymerized writing monomers.
Die geschriebenen Hologramme wurden nun auf folgende Weise ausgelesen. Der Shutter des Signalstrahls blieb geschlossen. Der Shutter des Referenzstrahls war geöffnet. Die Irisblende des Referenzstrahls wurde auf einen Durchmesser < 1mm geschlossen. Damit erreichte man, dass für alle Drehwinkel (Ω) des Mediums der Strahl immer vollständig im zuvor geschriebenen Hologramm lag. Der Drehtisch überstrich nun computergesteuert den Winkelbereich von Qmin bis Qmax mit einer Winkelschrittweite von 0.05°. Ω wird von der Probennormale zur Referenzrichtung des Drehtisches gemessen. Die Referenzrichtung des Drehtisches ergibt sich dann wenn beim Schreiben des Hologramms der Einfallswinkel des Referenz- und des Signalstrahls betragsmäßig gleich sind also α0 = -31.8° und β0 = 31.8° gilt. Dann beträgt Ωrecording = 0°. Für α0 = -21.8° und β0 = 41.8° beträgt Ωrecording daher 10°. Allgemein gilt für das Interferenzfeld beim Schreiben ("recording") des Hologramms:
In diesem Fall gilt also θ0 = -31.8°. An jedem angefahrenen Drehwinkel Ω wurden die Leistungen des in der nullten Ordnung transmittierten Strahls mittels des entsprechenden Detektors D und die Leistungen des in die erste Ordnung abgebeugten Strahls mittels des Detektors D gemessen. Die Beugungseffizienz ergab sich bei jedem angefahrenen Winkel Ω als der Quotient aus:
PD ist die Leistung im Detektor des abgebeugten Strahls und PT ist die Leistung im Detektor des transmittierten Strahls. P D is the power in the detector of the diffracted beam and P T is the power in the detector of the transmitted beam.
Mittels des oben beschriebenen Verfahrens wurde die Braggkurve, sie beschreibt den Beugungswirkungsgrad η in Abhängigkeit des Drehwinkels Ω, des geschriebenen Hologramms gemessen und in einem Computer gespeichert. Zusätzlich wurde auch die in die nullte Ordnung transmittierte Intensität gegen den Drehwinkel Ω aufgezeichnet und in einem Computer gespeichert.By means of the method described above, the Bragg curve, which describes the diffraction efficiency η as a function of the angle of rotation Ω, of the written hologram was measured and stored in a computer. In addition, the intensity transmitted in the zeroth order was also recorded against the angle of rotation Ω and stored in a computer.
Die maximale Beugungseffizienz (DE = ηmax) des Hologramms, also sein Spitzenwert, wurde bei Ωreconstruction ermittelt. Eventuell musste dazu die Position des Detektors des abgebeugten Strahls verändert werden, um diesen maximalen Wert zu bestimmen.The maximum diffraction efficiency (DE = η max ) of the hologram, ie its peak value, was determined during Ω reconstruction . It may be necessary to change the position of the detector of the diffracted beam to determine this maximum value.
Der Brechungsindexkontrast Δn und die Dicke d der Photopolymerschicht wurde nun mittels der Coupled Wave Theorie (siehe;
Alle geometrischen Größen, die sich auf das geschriebene Hologramm beziehen und nicht auf das Interferenzmuster werden als gestrichene Größen dargestellt.The refractive index contrast Δn and the thickness d of the photopolymer layer has now been determined by means of the coupled wave theory (cf.
All geometrical quantities related to the written hologram and not to the interference pattern are shown as primed quantities.
Für die Braggkurve η(Ω) eines Reflexionshologramms gilt nach Kogelnik:
Beim Auslesen des Hologramms ("reconstruction") gilt wie analog oben dargestellt:
An der Bragg-Bedingung ist das "Dephasing" DP = 0. Und es folgt entsprechend:
Der noch unbekannt Winkel β' kann aus dem Vergleich der Bragg-Bedingung des Interferenzfeldes beim Schreiben des Hologramms und der Bragg-Bedingung beim Auslesen des Hologramms ermittelt werden unter der Annahme, dass nur Dickenschwindung stattfindet. Dann folgt:
Die maximale Beugungseffizienz (DE = ηmax) ergibt sich dann für ξ = 0 zu:
Die Messdaten der Beugungseffizienz, die theoretische Braggkurve und die transmittierte Intensität werden wie in
Da DE bekannt ist wird die Form der theoretischen Braggkurve nach Kogelnik nur noch durch die Dicke d' der Photopolymerschicht bestimmt. Δn wird über DE für gegebene Dicke d' so nachkorrigiert, dass Messung und Theorie von DE immer übereinstimmen. d' wird nun solange angepasst bis die Winkelpositionen der ersten Nebenminima der theoretischen Braggkurve mit den Winkelpositionen der ersten Nebenmaxima der transmittierten Intensität übereinstimmen und zudem die volle Breite bei halber Höhe (FWHM) für die theoretische Braggkurve und für die transmittierte Intensität übereinstimmen.Since DE is known, the shape of the theoretical Bragg curve according to Kogelnik is determined only by the thickness d 'of the photopolymer layer. Δn is corrected over DE for a given thickness d ' so that the measurement and theory of DE are always the same. d ' is now adjusted until the angular positions of the first secondary minima of the theoretical Bragg curve coincide with the angular positions of the first secondary maxima of the transmitted intensity and, moreover, the full width at half height (FWHM) for the theoretical Bragg curve and for the transmitted intensity coincide.
Da die Richtung in der ein Reflexionshologramm bei der Rekonstruktion mittels eines Ω-Scans mitrotiert, der Detektor für das abgebeugte Licht aber nur einen endlichen Winkelbereich erfassen kann, wird die Braggkurve von breiten Holgrammen (kleines d') bei einem Ω-Scan nicht vollständig erfasst, sondern nur der zentrale Bereich, bei geeigneter Detektorpositionierung. Daher wird die zur Braggkurve komplementäre Form der transmittierten Intensität zur Anpassung der Schichtdicke d' zusätzlich herangezogen.Since the direction in which a reflection hologram co-rotates during the reconstruction by means of an Ω scan, but the detector for the diffracted light can detect only a finite angular range, the Bragg curve of broad fathoms (small d ') in an Ω-scan is not fully detected but only the central area, with appropriate detector positioning. Therefore, the complementary to the Bragg curve shape of the transmitted intensity to adjust the layer thickness d 'is additionally used.
Für eine Formulierung wurde diese Prozedur eventuell mehrfach für verschiedene Belichtungszeiten t an verschiedenen Medien wiederholt, um festzustellen bei welcher mittleren Energiedosis des einfallenden Laserstrahls beim Schreiben des Hologramms DE in den Sättigungswert übergeht. Die mittlere Energiedosis E ergibt sich wie folgt aus den Leistungen der zwei den Winkeln α0 und β0 zugeordneten Teilstrahlen (Referenzstrahl mit Pr = 0.50 mW und Signalstrahl mit Ps = 0.63 mW), der Belichtungszeit t und dem Durchmesser der Irisblende (0.4 cm):
Die Leistungen der Teilstrahlen wurden so angepasst, dass in dem Medium bei den verwendeten Winkeln ao und β0, die gleiche Leistungsdichte erreicht wird.The powers of the partial beams have been adjusted so that the same power density is achieved in the medium at the angles ao and β 0 used.
Die verwendeten Lösungsmittel und Reagenzien wurden im Chemikalienhandel bezogen.
Sofern nicht abweichend vermerkt beziehen sich alle Prozentangaben auf Gewichtsprozent.Unless otherwise noted, all percentages are by weight.
In einem 100 mL Rundkolben wurden 18.4 g BINOL, 0.08 g Desmorapid Z und 0.03 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Dichlormethan vorgelegt. Anschließend wurde eine 1:1 Mischung von 10.0 g KarenzMOI® und 9.1 g KarenzAOI® zugetropft und die Mischung bei Raumtemperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Dichlormethan befreit. Das Produkt wurde als farbloser Feststoff erhalten.18.4 g of BINOL, 0.08 g of Desmorapid Z and 0.03 g of 2,6-di-tert-butyl-4-methylphenol in 25 mL of dichloromethane were placed in a 100 mL round bottom flask. Subsequently, a 1: 1 mixture of 10.0 g KarenzMOI® and 9.1 g KarenzAOI® was added dropwise and the mixture stirred at room temperature until the isocyanate content had dropped below 0.1%. The product was then freed from dichloromethane in a rotary evaporator. The product was obtained as a colorless solid.
In einem 25 mL Rundkolben wurden 3.0 g Dimethyl 2,2'-dihydroxy-1,1'-binaphthyl-3,3'-dicarboxylat ([47644-69-9], hergestellt wie in
In einem 250 mL Rundkolben wurden 40.0 g BINOL, 0.18 g Desmorapid Z und 0.06 g 2,6-Di-tert.-butyl-4-methylphenol in 80 mL Dichlormethan vorgelegt. Anschließend wurden 39.4 g KarenzAOI® zugetropft und die Mischung bei Raumtemperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Dichlormethan befreit. Das Produkt wurde als farbloser Feststoff erhalten.40.0 g of BINOL, 0.18 g of Desmorapid Z and 0.06 g of 2,6-di-tert-butyl-4-methylphenol in 80 mL of dichloromethane were placed in a 250 mL round bottom flask. Subsequently, 39.4 g KarenzAOI® were added dropwise and the mixture was stirred at room temperature until the isocyanate content had dropped below 0.1%. The product was then freed from dichloromethane in a rotary evaporator. The product was obtained as a colorless solid.
In einem 100 mL Rundkolben wurden 12.0 g BINOL, 0.05 g Desmorapid Z und 0.02 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Dichlormethan vorgelegt. Anschließend wurden 13.0 g KarenzMOI® zugetropft und die Mischung bei Raumtemperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Dichlormethan befreit. Das Produkt wurde als farbloser Feststoff erhalten.12.0 g of BINOL, 0.05 g of Desmorapid Z and 0.02 g of 2,6-di-tert-butyl-4-methylphenol in 25 mL of dichloromethane were placed in a 100 mL round bottom flask. Subsequently, 13.0 g of KarenzMOI® were added dropwise and the mixture was stirred at room temperature until the isocyanate content had fallen below 0.1%. The product was then freed from dichloromethane in a rotary evaporator. The product was obtained as a colorless solid.
In einem 25 mL Rundkolben wurden 3.0 g 2,2'-Dihydroxy-1,1'-binaphthyl-6,6'-dicarbonitril ([164171-19-1], hergestellt aus 6-Cyan-2-naphthol wie in
In einem 25 mL Rundkolben wurden 2.5 g 6,6'-Dibromo-1,1'-binaphthyl-2,2'-diol ([80655-81-8], erhältlich von ABCR GmbH & Co. KG, Karlsruhe, Deutschland), 0.01 g Borchi® Kat 22 und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 10 mL Ethylacetat vorgelegt. Anschließend wurden 1.6 g KarenzAOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.2.5 g of 6,6'-dibromo-1,1'-binaphthyl-2,2'-diol ([80655-81-8], available from ABCR GmbH & Co. KG, Karlsruhe, Germany) were placed in a 25 mL round bottom flask. , 0.01 g Borchi® Kat 22 and 0.01 g of 2,6-di-tert-butyl-4-methylphenol in 10 mL of ethyl acetate. Subsequently, 1.6 g KarenzAOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 25 mL Rundkolben wurden 2.5 g 6,6'-Dibromo-1,1'-binaphthyl-2,2'-diol ([80655-81-8], erhältlich von ABCR GmbH & Co. KG, Karlsruhe, Deutschland), 0.01 g Borchi® Kat 22 und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 10 mL Ethylacetat vorgelegt. Anschließend wurden 1.7 g KarenzMOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.2.5 g of 6,6'-dibromo-1,1'-binaphthyl-2,2'-diol ([80655-81-8], available from ABCR GmbH & Co. KG, Karlsruhe, Germany) were placed in a 25 mL round bottom flask. , 0.01 g Borchi® Kat 22 and 0.01 g of 2,6-di-tert-butyl-4-methylphenol in 10 mL of ethyl acetate. Subsequently, 1.7 g KarenzMOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 25 mL Rundkolben wurden 3.0 g 7,7'-Dimethoxy-1,1'-binaphthyl-2,2'-diol ([128702-28-3], hergestellt aus 7-Methoxy-2-naphthol wie in
In einem 250 mL Rundkolben wurden 34.6 g BINOL und 0.09 g Borchi® Kat 22 in 50 mL Ethylacetat vorgelegt. Anschließend wurden 15.4 g Hexylisocyanat zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Es wurden 49.3 g 2'-Hydroxy-1,1'-binaphthyl-2-yl-hexylcarbamat als farbloser Feststoff erhalten.34.6 g BINOL and 0.09 g Borchi® Kat 22 in 50 mL ethyl acetate were placed in a 250 mL round bottom flask. Subsequently, 15.4 g of hexyl isocyanate were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. There were obtained 49.3 g of 2'-hydroxy-1,1'-binaphthyl-2-yl-hexylcarbamate as a colorless solid.
In einem 100 mL Rundkolben wurden 18.6 g 2'-Hydroxy-1,1'-binaphthyl-2-yl-hexylcarbamat, 0.03 g Borchi® Kat 22 und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 6.35 g KarenzAOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.18.6 g of 2'-hydroxy-1,1'-binaphthyl-2-yl hexylcarbamate, 0.03 g of Borchi® Kat 22 and 0.01 g of 2,6-di-tert-butyl-4-methylphenol in. Were placed in a 100 mL round bottom flask 25 mL of ethyl acetate. Subsequently, 6.35 g KarenzAOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 100 mL Rundkolben wurden 18.1 g 2'-Hydroxy-1,1'-binaphthyl-2-yl-hexylcarbamat (siehe Beispiel 9), 0.03 g Borchi® Kat 22 und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 6.81 g KarenzMOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.In a 100 mL round bottom flask, 18.1 g of 2'-hydroxy-1,1'-binaphthyl-2-yl-hexylcarbamate (see Example 9), 0.03 g of Borchi® Kat 22 and 0.01 g of 2,6-di-tert-butyl 4-methylphenol in 25 mL of ethyl acetate. Subsequently, 6.81 g KarenzMOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 250 mL Rundkolben wurden 35.3 g BINOL und 0.09 g Borchi® Kat 22 in 50 mL Ethylacetat vorgelegt. Anschließend wurden 14.7 g Phenylisocyanat zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Es wurden 49.2 g 2'-Hydroxy-1,1'-binaphthyl-2-yl-phenylcarbamat als farbloser Feststoff erhalten.35.3 g BINOL and 0.09 g Borchi® Kat 22 in 50 mL ethyl acetate were placed in a 250 mL round bottom flask. Subsequently, 14.7 g of phenyl isocyanate were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently the product was freed from ethyl acetate in a rotary evaporator. There were obtained 49.2 g of 2'-hydroxy-1,1'-binaphthyl-2-yl phenylcarbamate as a colorless solid.
In einem 100 mL Rundkolben wurden 18.5 g 2'-Hydroxy-1,1'-binaphthyl-2-yl-phenylcarbamat, 0.03 g Borchi® Kat 22 und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 6.44 g KarenzAOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.In a 100 mL round bottom flask, 18.5 g of 2'-hydroxy-1,1'-binaphthyl-2-yl-phenylcarbamate, 0.03 g of Borchi® Kat 22 and 0.01 g of 2,6-di-tert-butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 6.44 g KarenzAOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 100 mL Rundkolben wurden 18.0 g 2'-Hydroxy-1,1'-binaphthyl-2-yl-phenylcarbamat (siehe Beispiel 11), 0.03 g Borchi® Kat 22 und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 6.90 g KarenzMOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.In a 100 mL round bottom flask, 18.0 g of 2'-hydroxy-1,1'-binaphthyl-2-yl-phenylcarbamate (see Example 11), 0.03 g of Borchi® Kat 22 and 0.01 g of 2,6-di-tert-butyl 4-methylphenol in 25 mL of ethyl acetate. Subsequently, 6.90 g KarenzMOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 250 mL Rundkolben wurden 31.7 g BINOL und 0.08 g Borchi® Kat 22 in 50 mL Ethylacetat vorgelegt. Anschließend wurden 18.3 g 3-Methylthio-phenylisocyanat zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Es wurden 49.5 g 2'-Hydroxy-1,1'-binaphthyl-2-yl [3-(methylsulfanyl)phenyl]carbamat als farbloser Feststoff erhalten.31.7 g BINOL and 0.08 g Borchi® Kat 22 in 50 mL ethyl acetate were placed in a 250 mL round bottom flask. Subsequently, 18.3 g of 3-methylthio-phenyl isocyanate were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. There were obtained 49.5 g of 2'-hydroxy-1,1'-binaphthyl-2-yl [3- (methylsulfanyl) phenyl] carbamate as a colorless solid.
In einem 100 mL Rundkolben wurden 19.0 g 2'-Hydroxy-1,1'-binaphthyl-2-yl [3-(methylsulfanyl)phenyl]carbamat, 0.03 g Borchi® Kat 22 und 0.02 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetatvorgelegt. Anschließend wurden 5.94 g KarenzAOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.In a 100 mL round bottomed flask, 19.0 g of 2'-hydroxy-1,1'-binaphthyl-2-yl [3- (methylsulfanyl) phenyl] carbamate, 0.03 g of Borchi® Kat 22 and 0.02 g of 2,6-di-tert. -butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 5.94 g KarenzAOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 100 mL Rundkolben wurden 18.6 g 2'-Hydroxy-1,1'-binaphthyl-2-yl [3-(methylsulfanyl)phenyl]carbamat (siehe Beispiel 13), 0.03 g Borchi® Kat 22 und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 6.38 g KarenzMOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.In a 100 mL round bottomed flask were added 18.6 g of 2'-hydroxy-1,1'-binaphthyl-2-yl [3- (methylsulfanyl) phenyl] carbamate (see Example 13), 0.03 g of Borchi® Kat 22 and 0.01 g of 2.6 -Di-tert-butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 6.38 g KarenzMOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 250 mL Rundkolben wurden 27.8 g BINOL und 0.07 g Borchi® Kat 22 in 50 mL Ethylacetat vorgelegt. Anschließend wurden 22.1 g 2-Isocyanatophenyl-phenyl-sulfid ([13739-55-4] zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Es wurden 48.9 g 2'-Hydroxy-1,1'-binaphthyl-2-yl [2-(phenylsulfanyl)-phenyl]carbamat als farbloser Feststoff erhalten.27.8 g of BINOL and 0.07 g of Borchi® Kat 22 in 50 mL of ethyl acetate were placed in a 250 mL round bottom flask. Subsequently, 22.1 g of 2-isocyanatophenyl-phenyl-sulfide ([13739-55-4] were added dropwise and the mixture was stirred at 80 ° C. until the isocyanate content had fallen below 0.1%, after which the product was freed from ethyl acetate on a rotary evaporator 48.9 g of 2'-hydroxy-1,1'-binaphthyl-2-yl [2- (phenylsulfanyl) -phenyl] carbamate as a colorless solid.
In einem 100 mL Rundkolben wurden 19.6 g 2'-Hydroxy-1,1'-binaphthyl-2-yl [2-(phenylsulfanyl)phenyl]carbamat, 0.03 g Borchi® Kat 22 und 0.02 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetatvorgelegt. Anschließend wurden 5.38 g KarenzAOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.In a 100 mL round bottomed flask, 19.6 g of 2'-hydroxy-1,1'-binaphthyl-2-yl [2- (phenylsulfanyl) phenyl] carbamate, 0.03 g of Borchi® Kat 22 and 0.02 g of 2,6-di-tert. -butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 5.38 g KarenzAOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 100 mL Rundkolben wurden 19.2 g 2'-Hydroxy-1,1'-binaphthyl-2-yl [2-(phenylsulfanyl)phenyl]carbamat (siehe Beispiel 15), 0.03 g Borchi® Kat 22 und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 5.79 g KarenzMOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.In a 100 mL round bottom flask, 19.2 g of 2'-hydroxy-1,1'-binaphthyl-2-yl [2- (phenylsulfanyl) phenyl] carbamate (see Example 15), 0.03 g of Borchi® Kat 22 and 0.01 g of 2.6 -Di-tert-butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 5.79 g KarenzMOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 250 mL Rundkolben wurden 31.4 g BINOL und 0.08 g Borchi® Kat 22 in 50 mL Ethylacetat vorgelegt. Anschließend wurden 18.5 g 1-Naphtylisocyanat zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Es wurden 49.1 g 2'-Hydroxy-1,1'-binaphthyl-2-yl 1-naphthylcarbamat als farbloser Feststoff erhalten.31.4 g BINOL and 0.08 g Borchi® Kat 22 in 50 mL ethyl acetate were placed in a 250 mL round bottom flask. Subsequently, 18.5 g of 1-Naphtylisocyanat were added dropwise and the mixture stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. This gave 49.1 g of 2'-hydroxy-1,1'-binaphthyl-2-yl 1-naphthylcarbamate as a colorless solid.
In einem 100 mL Rundkolben wurden 19.0 g 2'-Hydroxy-1,1'-binaphthyl-2-yl [2-(phenylsulfanyl)phenyl]carbamat, 0.03 g Borchi® Kat 22 und 0.02 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetatvorgelegt. Anschließend wurden 5.90 g KarenzAOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.In a 100 mL round bottomed flask, 19.0 g of 2'-hydroxy-1,1'-binaphthyl-2-yl [2- (phenylsulfanyl) phenyl] carbamate, 0.03 g of Borchi® Kat 22 and 0.02 g of 2,6-di-tert. -butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 5.90 g KarenzAOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 100 mL Rundkolben wurden 18.6 g 2'-Hydroxy-1,1'-binaphthyl-2-yl 1-naphthylcarbamat (siehe Beispiel 17), 0.03 g Borchi® Kat 22 und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 6.34 g KarenzMOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.18.6 g of 2'-hydroxy-1,1'-binaphthyl-2-yl 1-naphthylcarbamate (see Example 17), 0.03 g of Borchi® Kat 22 and 0.01 g of 2,6-di-tert. butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 6.34 g KarenzMOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 250 mL Rundkolben wurden 37.2 g BINOL in 150 g Ethylacetat bei 80 °C vorgelegt und 0.005 g Desmorapid Z zugegeben. Unter intensivem Rühren wurden 10.7 g Hexamethylen-diisocyanat (Desmodur H, Produkt von Bayer MaterialScience AG, NCO-Gehalt >49.7%) zugegeben und solange bei dieser Temperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Das so erhaltene Bis(2'-hydroxy-1,1'-binaphthyl-2-yl) hexan-1,6-diylbiscarbamat hatte einen Festkörpergehalt von 24.2% in Ethylacetat.37.2 g of BINOL in 150 g of ethyl acetate at 80 ° C. were introduced into a 250 ml round-bottom flask and 0.005 g of Desmorapid Z were added. With vigorous stirring, 10.7 g of hexamethylene diisocyanate (Desmodur H, product of Bayer MaterialScience AG, NCO content> 49.7%) were added and the mixture was stirred at this temperature until the isocyanate content had dropped below 0.1%. The bis (2'-hydroxy-1,1'-binaphthyl-2-yl) hexane-1,6-diylbiscarbamate thus obtained had a solids content of 24.2% in ethyl acetate.
Zu 61.2g der obigen Lösung von Bis(2'-hydroxy-1,1'-binaphthyl-2-yl) hexan-1,6-diylbiscarbamat in Ethylacetat wurden unter Durchleitung von Luft bei 80 °C 5.6 g KarenzAOI® getropft und solange bei dieser Temperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloses Öl erhalten.To 61.2 g of the above solution of bis (2'-hydroxy-1,1'-binaphthyl-2-yl) hexane-1,6-diylbiscarbamate in ethyl acetate was added 5.6 g of KarenzAOI® while passing air at 80 ° C dropped and stirred at this temperature until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless oil.
Zu 61.2 g der Lösung von Bis(2'-hydroxy-1,1'-binaphthyl-2-yl) hexan-1,6-diylbiscarbamat in Ethylacetat (siehe Beispiel 19) wurden unter Durchleitung von Luft bei 80 °C 6.2 g KarenzMOI® getropft und solange bei dieser Temperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloses Öl erhalten.To 61.2 g of the solution of bis (2'-hydroxy-1,1'-binaphthyl-2-yl) hexane-1,6-diylbiscarbamate in ethyl acetate (see Example 19) while passing air at 80 ° C 6.2 g KarenzMOI ® and stirred at this temperature until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless oil.
In einem 250 mL Rundkolben wurden 40.1 g BINOL in 150 g Ethylacetat bei 80 °C vorgelegt und 0.005 g Desmorapid Z zugegeben. Unter intensivem Rühren wurden 14.5 g Trimethylhexamethylendiisocyanat (Vestanat TMDI, Produkt von Evonik Industries, NCO-Gehalt = 40.0%) zugegeben und solange bei dieser Temperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Das so erhaltene Bis(2'-hydroxy-1,1'-binaphthyl-2-yl) (2,2,4-trimethylhexan-1,6-diyl)biscarbamat hatte einen Festkörpergehalt von 26.7% in Ethylacetat.40.1 g of BINOL in 150 g of ethyl acetate at 80 ° C. were introduced into a 250 mL round bottom flask and 0.005 g of Desmorapid Z were added. With vigorous stirring, 14.5 g of trimethylhexamethylene diisocyanate (Vestanat TMDI, product of Evonik Industries, NCO content = 40.0%) were added and the mixture was stirred at this temperature until the isocyanate content had fallen below 0.1%. The bis (2'-hydroxy-1,1'-binaphthyl-2-yl) (2,2,4-trimethylhexane-1,6-diyl) biscarbamate thus obtained had a solids content of 26.7% in ethyl acetate.
Zu 58.7 g der obigen Lösung von Bis(2'-hydroxy-1,1'-binaphthyl-2-yl) (2,2,4-trimethylhexan-1,6-diyl)biscarbamat in Ethylacetat wurden unter Durchleitung von Luft bei 80 °C 5.6 g KarenzAOI® getropft und solange bei dieser Temperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloses Öl erhalten.To 58.7 g of the above solution of bis (2'-hydroxy-1,1'-binaphthyl-2-yl) (2,2,4-trimethylhexane-1,6-diyl) biscarbamate in ethyl acetate was added while passing air through 80 ° C 5.6 g KarenzAOI® and stirred at this temperature until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless oil.
Zu 58.7 g der Lösung von Bis(2'-hydroxy-1,1'-binaphthyl-2-yl) (2,2,4-trimethylhexan-1,6-diyl)biscarbamat in Ethylacetat (siehe Beispiel 21) wurden unter Durchleitung von Luft bei 80 °C 6.2 g KarenzMOI® getropft und solange bei dieser Temperatur gerührt, bis der Iso- cyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloses Öl erhalten.To 58.7 g of the solution of bis (2'-hydroxy-1,1'-binaphthyl-2-yl) (2,2,4-trimethylhexane-1,6-diyl) biscarbamate in ethyl acetate (see Example 21) was added of air at 80 ° C., 6.2 g of KarenzMOI® are added dropwise and the mixture is stirred at this temperature until the iso- cyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless oil.
In einem 250 mL Rundkolben wurden 40.1 g BINOL in 150 g Ethylacetat bei 80 °C vorgelegt und 0.005 g Desmorapid Z zugegeben. Unter intensivem Rühren wurden 15.2 g 3-Isocyanatomethyl-3,5,5-tiimethylcyclohexylisocyanat (Desmodur I, Isophorondiisocyanat (IPDI) Produkt von Bayer MaterialScience AG, NCO-Gehalt >37.5%) zugegeben und solange bei dieser Temperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Das so erhaltene 2'-Hydroxy-1,1'-binaphthyl-2-yl {3-[({[(2'-hydroxy-1,1'-binaphthyl-2-yl)oxy]carbonyl}amino)methyl]-3,5,5-trimethylcyclohexyl}carbamat hatte einen Festkörpergehalt von 26.9% in Ethylacetat.40.1 g of BINOL in 150 g of ethyl acetate at 80 ° C. were introduced into a 250 mL round bottom flask and 0.005 g of Desmorapid Z were added. With vigorous stirring, 15.2 g of 3-isocyanatomethyl-3,5,5-tiimethylcyclohexylisocyanat (Desmodur I, isophorone diisocyanate (IPDI) product of Bayer MaterialScience AG, NCO content> 37.5%) was added and stirred at this temperature until the isocyanate content 0.1% had dropped. The thus-obtained 2'-hydroxy-1,1'-binaphthyl-2-yl {3 - [({[(2'-hydroxy-1,1'-binaphthyl-2-yl) oxy] carbonyl} amino) methyl] -3,5,5-trimethylcyclohexyl} carbamate had a solids content of 26.9% in ethyl acetate.
Zu 59.1 g der obigen Lösung von 2'-Hydroxy-1,1'-binaphthyl-2-yl{3-[({[(2'-hydroxy-1,1'-binaphthyl-2-yl)oxy]carbonyl}amino)methyl]-3,5,5-trimethylcyclohexyl}carbamat in Ethylacetat wurden unter Durchleitung von Luft bei 80 °C 5.6 g KarenzAOI® getropft und solange bei dieser Temperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloses Öl erhalten.To 59.1 g of the above solution of 2'-hydroxy-1,1'-binaphthyl-2-yl {3 - [({[(2'-hydroxy-1,1'-binaphthyl-2-yl) oxy] carbonyl} amino) methyl] -3,5,5-trimethylcyclohexyl} carbamate in ethyl acetate were added dropwise while passing air at 80 ° C 5.6 g KarenzAOI® and stirred at this temperature until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless oil.
Zu 59.1 g der Lösung von 2'-Hydroxy-1,1'-binaphthyl-2-yl{3-[({[(2'-hydroxy-1,1'-binaphthyl-2-yl)oxy]carbonyl}amino)methyl]-3,5,5-trimethylcyclohexyl} carbamat in Ethylacetat (siehe Beispiel 23) wurden unter Durchleitung von Luft bei 80 °C 6.2 g KarenzMOI® getropft und solange bei dieser Temperatur gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloses Öl erhalten.To 59.1 g of the solution of 2'-hydroxy-1,1'-binaphthyl-2-yl {3 - [({[(2'-hydroxy-1,1'-binaphthyl-2-yl) oxy] carbonyl} amino ) Methyl] -3,5,5-trimethylcyclohexyl} carbamate in ethyl acetate (see Example 23) were added dropwise while passing air at 80 ° C 6.2 g KarenzMOI® and stirred at this temperature until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless oil.
In einem Becherglas wurden 16.0 g 2-Naphthol, 22.5 g 6-Brom-2-naphthol und 1.5 g CuCl(OH)*TMEDA (hergestellt wie in
4.41 g 6-Brom-1,1'-binaphthyl-2,2'-diol wurden mit 0.015 g Desmorapid Z und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 3.41 g KarenzAOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1% gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.4.41 g of 6-bromo-1,1'-binaphthyl-2,2'-diol were charged with 0.015 g Desmorapid Z and 0.01 g of 2,6-di-tert-butyl-4-methylphenol in 25 mL of ethyl acetate. Then 3.41 g KarenzAOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
4.23 g 6-Brom-1,1'-binaphthyl-2,2'-diol (Herstellung siehe Beispiel 25) wurden mit 0.015 g Desmorapid Z und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 3.59 g KarenzMOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.4.23 g of 6-bromo-1,1'-binaphthyl-2,2'-diol (preparation see Example 25) were mixed with 0.015 g of Desmorapid Z and 0.01 g of 2,6-di-tert-butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 3.59 g KarenzMOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem Becherglas wurden 20.8 g 2-Naphtol, 22.2 g 6-Cyan-2-Naphthol und 1.5 g CuCl(OH)*TMEDA (hergestellt wie in
4.10 g 6-Cyan-1,1'-binaphthyl-2,2'-diol wurden mit 0.015 g Desmorapid Z und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 3.72 g KarenzAOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.4.10 g of 6-cyano-1,1'-binaphthyl-2,2'-diol were charged with 0.015 g Desmorapid Z and 0.01 g of 2,6-di-tert-butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 3.72 g KarenzAOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
3.92 g 6-Cyan-1,1'-binaphthyl-2,2'-diol (Herstellung siehe Beispiel 27) wurden mit 0.015 g Desmorapid Z und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 3.90 g KarenzMOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.3.92 g of 6-cyano-1,1'-binaphthyl-2,2'-diol (preparation see Example 27) were mixed with 0.015 g Desmorapid Z and 0.01 g of 2,6-di-tert-butyl-4-methylphenol in 25 mL of ethyl acetate. Subsequently, 3.90 g KarenzMOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem Becherglas wurden 22.8 g 6-Brom-2-Naphtol, 15.8 g 6-Cyan-2-Naphthol und 1.4 g CuCl(OH)*TMEDA (hergestellt wie in
4.54 g 6'-Brom-2,2'-dihydroxy-1,1'-binaphthyl-6-carbonitril wurden mit 0.015 g Desmorapid Z und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 3.28 g KarenzAOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.4.54 g of 6'-bromo-2,2'-dihydroxy-1,1'-binaphthyl-6-carbonitrile were mixed with 0.015 g Desmorapid Z and 0.01 g of 2,6-di-tert-butyl-4-methylphenol in 25 mL Submitted ethyl acetate. Subsequently, 3.28 g KarenzAOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
4.36 g 6'-Brom-2,2'-dihydioxy-1,1'-binaphthyl-6-carbonitril (Herstellung siehe Beispiel 29) wurden mit 0.015 g Desmorapid Z und 0.01 g 2,6-Di-tert.-butyl-4-methylphenol in 25 mL Ethylacetat vorgelegt. Anschließend wurden 3.46 g KarenzMOI® zugetropft und die Mischung bei 80 °C gerührt, bis der Isocyanatgehalt unter 0.1 % gesunken war. Anschließend wurde das Produkt im Rotationsverdampfer vom Ethylacetat befreit. Das Produkt wurde als farbloser Feststoff erhalten.4.36 g of 6'-bromo-2,2'-dihydioxy-1,1'-binaphthyl-6-carbonitrile (preparation see Example 29) were mixed with 0.015 g Desmorapid Z and 0.01 g of 2,6-di-tert-butyl- 4-methylphenol in 25 mL of ethyl acetate. Subsequently, 3.46 g KarenzMOI® were added dropwise and the mixture was stirred at 80 ° C until the isocyanate content had dropped below 0.1%. Subsequently, the product was freed from ethyl acetate on a rotary evaporator. The product was obtained as a colorless solid.
In einem 1 L Kolben wurden 0.18 g Zinnoctoat, 374.8 g ε-Caprolacton und 374.8 g eines difunktionellen Polytetrahydrofuranpolyetherpolyols (Equivalentgewicht 500 g/Mol OH) vorgelegt und auf 120 °C aufgeheizt und so lange auf dieser Temperatur gehalten, bis der Festgehalt (Anteil der nicht-flüchtigen Bestandteile) bei 99.5 Gew.-% oder darüber lag. Anschließend wurde abgekühlt und das Produkt als wachsiger Feststoff erhalten.0.18 g of tin octoate, 374.8 g of ε-caprolactone and 374.8 g of a difunctional polytetrahydrofuranpolyether polyol (equivalent weight 500 g / mol OH) were placed in a 1 l flask and heated to 120 ° C. and kept at this temperature until the solids content (proportion of non-volatile ingredients) was 99.5% by weight or above. It was then cooled and the product obtained as a waxy solid.
In einem 100 mL Rundkolben wurden 0.02 g 2,6-Di-tert.-butyl-4-methylphenol, 0.01 g Desmorapid Z, 11.7 g 3-(Methylthio)phenylisocyanat [28479-1-8] vorgelegt und auf 60 °C erwärmt. Anschließend wurden 8.2 g 2-Hydroxyethylacrylat zugetropft und die Mischung weiter auf 60 °C gehalten, bis der Isocyanatgehalt unter 0.1 % gesunken war. Danach wurde abgekühlt. Das Produkt wurde als farblose Flüssigkeit erhalten.0.02 g of 2,6-di-tert-butyl-4-methylphenol, 0.01 g of Desmorapid Z, 11.7 g of 3- (methylthio) phenyl isocyanate [28479-1-8] were introduced into a 100 ml round-bottomed flask and heated to 60.degree , Subsequently, 8.2 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was kept at 60 ° C until the isocyanate content had dropped below 0.1%. It was then cooled. The product was obtained as a colorless liquid.
In einem 50 mL Rundkolben wurden 0.02 g Desmorapid Z und 3.6 g Vestanat TMDI vorgelegt und auf 60 °C erwärmt. Anschließend wurden 11.9 g 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluorheptan-1-ol zugetropft und die Mischung weiter auf 60 °C gehalten, bis der Isocyanatgehalt unter 0.1 % gesunken war. Danach wurde abgekühlt. Das Produkt wurde als farbloses Öl erhalten.0.02 g Desmorapid Z and 3.6 g Vestanat TMDI were placed in a 50 mL round bottom flask and heated to 60 ° C. Subsequently, 11.9 g of 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptan-1-ol were added dropwise and the mixture was kept at 60 ° C until the isocyanate content was below 0.1%. had sunk. It was then cooled. The product was obtained as a colorless oil.
In einem 500 mL Rundkolben wurden 0.1 g 2,6-Di-tert.-butyl-4-methylphenol, 0.05 g Dibutylzinndilaurat sowie und 213.07 g einer 27 %-igen Lösung von Tris(p-isocyanatophenyl)thiophosphat in Ethylacetat (Desmodur® RFE, Produkt der Bayer MaterialScience AG, Leverkusen, Deutschland) vorgelegt und auf 60 °C erwärmt. Anschließend wurden 42.37 g 2-Hydroxyethylacrylat zugetropft und die Mischung weiter auf 60 °C gehalten, bis der Isocyanatgehalt unter 0.1 % gesunken war. Danach wurde abgekühlt und das Ethylacetat im Vakuum vollständig entfernt. Das Produkt wurde als teilkristalliner Feststoff erhalten.In a 500 mL round bottom flask, 0.1 g of 2,6-di-tert-butyl-4-methylphenol, 0.05 g of dibutyltin dilaurate and 213.07 g of a 27% solution of tris (p-isocyanatophenyl) thiophosphate in ethyl acetate (Desmodur® RFE , Product of Bayer MaterialScience AG, Leverkusen, Germany) and heated to 60 ° C. Subsequently, 42.37 g of 2-hydroxyethyl acrylate were added dropwise and the mixture was kept at 60 ° C until the isocyanate content had dropped below 0.1%. It was then cooled and the ethyl acetate was completely removed in vacuo. The product was obtained as a partially crystalline solid.
430.2 g Denacol EX 142 (Nagase-Chemtex, Japan), 129.7 g Acrylsäure, 1.18 g Triphenylphosphin und 0.006 g 2,6-Di-t.-butyl-4-methylphenol wurden in einem Dreihalskolben mit Rückflusskühler und Rührwerk vorgelegt. Zudem wurde Luft langsam durchgeleitet und auf 60 °C temperiert. Anschließend wird für 24 Stunden bei 90 °C gerührt. Man erhielt eine klare Flüssigkeit mit OH-Zahl = 157.8 mg KOH/g. 21.3 g dieses Zwischenprodukts und 5.2 g eines Gemischs aus 2,4- und 2,6- Tolylidendiisocyanat (Desmodur T80, Bayer MaterialScience AG, Leverkusen, Germany) wurden in einem Dreihalskolben mit Rückflusskühler und Rührwerk vorgelegt. Zudem wurde Luft langsam durchgeleitet und auf 60 °C temperiert. Nach anfänglicher Exothermie wurde das Produkt für 24 Stunden bei 60 °C gerührt. Es wurde ein klares, farbloses, gläsernes Produkt mit NCO = 0% erhalten.430.2 g of Denacol EX 142 (Nagase-Chemtex, Japan), 129.7 g of acrylic acid, 1.18 g of triphenylphosphine and 0.006 g of 2,6-di-t-butyl-4-methylphenol were placed in a three-necked flask with reflux condenser and stirrer. In addition, air was passed slowly and tempered to 60 ° C. The mixture is then stirred for 24 hours at 90 ° C. A clear liquid with OH number = 157.8 mg KOH / g was obtained. 21.3 g of this intermediate and 5.2 g of a mixture of 2,4- and 2,6-tolylene diisocyanate (Desmodur T80, Bayer MaterialScience AG, Leverkusen, Germany) were placed in a three-necked flask with reflux condenser and stirrer. In addition, air was passed slowly and tempered to 60 ° C. After initial exotherm, the product was stirred for 24 hours at 60 ° C. A clear, colorless, glassy product with NCO = 0% was obtained.
3.38 g der Polyol-Komponente 1 wurden mit 2.00 g Beispiel 1 gemäß Formel (I), 2.00 g Urethanacrylat 2, 1.50 g Additiv 1, 0.10 g CGI 909, 0.026 g Farbstoff 1 und 0.35 g N-Ethylpyrrolidon bei 60 °C gemischt, so dass eine klare Lösung erhalten wurde. Anschließend wurde auf 30 °C abgekühlt, 0.65 g Desmodur® N3900 zugegeben und erneut gemischt. Schließlich wurden 0.01 g Fomrez UL 28 zugegeben und erneut kurz gemischt. Die erhaltene, flüssige Masse wurde dann auf eine Glasplatte gegeben und dort mit einer zweiten Glasplatte abgedeckt. Dieser Probenkörper wurde 12 Stunden bei Raumtemperatur liegen gelassen und gehärtet.3.38 g of the polyol component 1 were mixed with 2.00 g of Example 1 according to formula (I), 2.00 g of urethane acrylate 2, 1.50 g of additive 1, 0.10 g of CGI 909, 0.026 g of dye 1 and 0.35 g of N-ethylpyrrolidone at 60 ° C, so that a clear solution was obtained. It was then cooled to 30 ° C, 0.65 g Desmodur® N3900 added and mixed again. Finally, 0.01 g of Fomrez UL 28 was added and mixed again briefly. The resulting liquid mass was then placed on a glass plate and there with a second glass plate covered. This sample was left for 12 hours at room temperature and cured.
Die Beispiel-Medien II - IX wurde hergestellt wie unter Beispiel-Medium I beschrieben. Es wurde - wie in Tabelle 1 aufgelistet - Beispiel 1 gegen das in der jeweiligen Zeile aufgeführte Beispiel in gleichem Gewichts-Anteil ersetzt.Example media II-IX were prepared as described under Example Medium I. It was - as listed in Table 1 - Example 1 replaced by the example listed in each row in the same weight proportion.
3.38 g der Polyol-Komponente 1 wurden mit 2.00 g Vergleichsbeispiel 1, 2.00 g Urethanacrylat 1, 1.50 g Additiv 1, 0.10 g CGI 909, 0.010 g Farbstoff 1 und 0.35 g N-Ethylpyrrolidon bei 60 °C gemischt, so dass eine klare Lösung erhalten wurde. Anschließend wurde auf 30 °C abgekühlt, 0.65 g Desmodur® N3900 zugegeben und erneut gemischt. Schließlich wurden 0.01 g Fomrez UL 28 zugegeben und erneut kurz gemischt. Die erhaltene, flüssige Masse wurde dann auf eine Glasplatte gegeben und dort mit einer zweiten Glasplatte abgedeckt. Dieser Probenkörper wurde 12 Stunden bei Raumtemperatur liegen gelassen und gehärtet.3.38 g of the polyol component 1 were mixed with 2.00 g of Comparative Example 1, 2.00 g of urethane acrylate 1, 1.50 g of additive 1, 0.10 g of CGI 909, 0.010 g of dye 1 and 0.35 g of N-ethylpyrrolidone at 60 ° C, so that a clear solution was obtained. It was then cooled to 30 ° C, 0.65 g Desmodur® N3900 added and mixed again. Finally, 0.01 g of Fomrez UL 28 was added and mixed again briefly. The resulting liquid mass was then placed on a glass plate and covered with a second glass plate. This sample was left for 12 hours at room temperature and cured.
3.38 g der Polyol-Komponente 1 wurden mit 2.00 g Vergleichsbeispiel 2, 2.00 g Urethanacrylat 1, 1.50 g Additiv 1, 0.10 g CGI 909, 0.010 g Farbstoff 1 und 0.35 g N-Ethylpyrrolidon bei 60 °C gemischt, so dass eine klare Lösung erhalten wurde. Anschließend wurde auf 30 °C abgekühlt, 0.65 g Desmodur® N3900 zugegeben und erneut gemischt. Schließlich wurden 0.01 g Fomrez UL 28 zugegeben und erneut kurz gemischt. Die erhaltene, flüssige Masse wurde dann auf eine Glasplatte gegeben und dort mit einer zweiten Glasplatte abgedeckt. Dieser Probenkörper wurde 12 Stunden bei Raumtemperatur liegen gelassen und gehärtet.3.38 g of the polyol component 1 were mixed with 2.00 g of Comparative Example 2, 2.00 g of urethane acrylate 1, 1.50 g of additive 1, 0.10 g of CGI 909, 0.010 g of dye 1 and 0.35 g of N-ethylpyrrolidone at 60 ° C, so that a clear solution was obtained. It was then cooled to 30 ° C, 0.65 g Desmodur® N3900 added and mixed again. Finally, 0.01 g of Fomrez UL 28 was added and mixed again briefly. The resulting liquid mass was then placed on a glass plate and covered with a second glass plate. This sample was left for 12 hours at room temperature and cured.
Die Bestimmung der Brechungsindexmodulation Δn in einem holographisch belichteten Photopolymer nach dem oben beschriebenen Verfahren gelingt am genauesten, wenn die Beugungseffizienz nicht völlig gesättigt sondern nahe bei 100% ist. Die Beugungseffizienz DE hängt dabei vom Produkt aus Δn und Schichtdicke d des Photopolymers ab. Bei den hier erhaltenen sehr hellen Hologrammen, die einen sehr hohen Brechungsindexkontrast Δn aufweisen, ist daher die Herstellung von Probekörpern mit sehr dünner Schichtdicke d erforderlich. Dazu wurde ein ausgewähltes Beispiel (Beispiel 3) in einer kontinuierlichen Beschichtungsanlage zu einem Photopolymer verarbeitet.The determination of the refractive index modulation Δn in a holographically exposed photopolymer according to the method described above succeeds most accurately when the diffraction efficiency is not completely saturated but close to 100%. The diffraction efficiency DE depends on the product of Δn and the layer thickness d of the photopolymer. For the very light holograms obtained here, which have a very high refractive index contrast Δn, it is therefore necessary to produce specimens with a very thin layer thickness d. For this purpose, a selected example (Example 3) was processed in a continuous coating plant to a photopolymer.
- 1a, b
- Vorratsbehälter
- 2a, b
- Dosiereinrichtung
- 3a, b
- Vakuumentgasungseinrichtung
- 4a, b
- Filter
- 5
- Statischer Mischer
- 6
- Beschichtungseinrichtung
- 7
- Umlufttrockner
- 8
- Trägersubstrat
- 9
- Abdeckschicht
- 1a, b
- reservoir
- 2a, b
- metering
- 3a, b
- Vakuumentgasungseinrichtung
- 4a, b
- filter
- 5
- Static mixer
- 6
- coater
- 7
- Umlufttrockner
- 8th
- carrier substrate
- 9
- covering
Zur Herstellung der Photopolymer-Formulierung wurden in einem Rührbehälter 45.7 g Polyol 1 schrittweise mit 290.0 g Ethylacetat, 20.0 g Beispiel 1, 60.0 g Urethan-acrylat 1, 60.0 g Additiv 1, 0.10 g Fomrez UL 28, 1.80 g BYK® 310 und 0.52 g Farbstoff 1 versetzt und gemischt, so dass eine klare Lösung erhalten wurde. Dieses Gemisch wurde in den Vorratsbehälter 1a der Beschichtungsanlage eingebracht. In den zweiten Vorratsbehälter 1b wurde eine separat hergestellte klare Mischung aus 3.0 g CGI 909, 8.87 g Desmodur N 3900 und 2.22 g Butylacetat eingefüllt. Beide Komponenten wurden dann jeweils durch die Dosiereinrichtungen 2a und 2b im Verhältnis von 16.3 zu 1 (Vorratsbehälter la zu 1b) zu den Vakuumentgasungseinrichtungen 3a und 3b gefördert und entgast. Von hier aus wurden sie dann jeweils durch die Filter 4a und 4b in den statischen Mischer 5 geleitet, in dem die Vermischung der Komponenten zur Photopolymer-Formulierung erfolgte. Die erhaltene, flüssige Masse wurde dann im Dunklen der Beschichtungseinrichtung 6 zugeführt.To prepare the photopolymer formulation, 45.7 g of polyol 1 were gradually added in a stirred vessel containing 290.0 g of ethyl acetate, 20.0 g of Example 1, 60.0 g of urethane acrylate 1, 60.0 g of additive 1, 0.10 g of Fomrez UL 28, 1.80 g of BYK® 310 and 0.52 g dye 1 was added and mixed, so that a clear solution was obtained. This mixture was introduced into the
Bei der Beschichtungseinrichtung 6 handelte es sich im vorliegenden Fall um eine dem Fachmann bekannte Schlitzdüse. Alternativ kann aber auch ein Rakelsystem (Doctor Blade) oder ein Rollenantragssystem zum Einsatz kommen. Mit Hilfe der Beschichtungseinrichtung 6 wurde die Photopolymer-Formulierung bei einer Verarbeitungstemperatur von 20 °C auf ein Trägersubstrat 8 in der Form einer 36 µm dicke Polyethylenterephthalatfolie appliziert und für 5.8 Minuten bei einer Vernetzungstemperatur von 80°C in einem Umlufttrockner 7 getrocknet. Dabei wurde ein Medium in der Form eines Films erhalten, der dann mit einer 40 µm Polyethylenfolie als Abdeckschicht 9 versehen und aufgewickelt wurde.The
Die erzielte Schichtdicke des Films beträgt 6 - 8 µm.The achieved layer thickness of the film is 6 - 8 microns.
Die wie beschrieben hergestellten Medien wurden mittels einer Messordnung gemäß
Die gefundenen Werte für die Beispiel-Medien I bis IX zeigen, dass die in den Photopolymer-Formulierungen eingesetzten erfindungsgemäßen Verbindungen der Formel (I) für die Verwendung in holographischen Medien mit sehr hoher Brechungsindexmodulation An sehr gut geeignet sind. Die Vergleichs-Medien V-1 und V-2 weisen keine erfindungsgemäßen Verbindung der Formel (I) auf und weisen in holographischen Medien geringere Werte für Δn auf. Mit dem Beispiel-Medium X kann gezeigt werden, dass die eingesetzten erfindungsgemäßen Verbindungen der Formel (I) eine sehr hohe Brechungsindexmodulation Δn aufweisen. The values found for the example media I to IX show that the compounds of the formula (I) according to the invention used in the photopolymer formulations are very suitable for use in holographic media with very high refractive index modulation An. The comparative media V-1 and V-2 have no inventive Compound of formula (I) and have lower values for Δn in holographic media. It can be shown with the example medium X that the compounds of the formula (I) used according to the invention have a very high refractive index modulation Δn.
Claims (15)
- Compound of formula (I)a) which is substituted at at least one of the carbon atoms 1, 2, 3, 4, 5, 6, 7, 8 with a moiety Racryl of formula (II)R1 is hydrogen or a (C1-C6)-alkyl group,X is a carboxamide (-C(O)N-) or a carboxylic ester (-C(O)O-) or a sulphonamide (-SO2N-) group,Y is a saturated or unsaturated or linear or branched optionally substituted moiety having 2-10 carbon atoms or a polyether having from one up to five (-CH2-CH2-O-)- or (-C(CH3)H-CH2-O-)- groups or a polyamine having from one to five nitrogen atoms, andZ is oxygen or sulphur,b) and the compound of formula (I) is at not less than one further carbon atom, 1, 2, 3, 4, 5, 6, 7, 8 substituted with a moiety of formula (III)
the carbon atoms of the compound of formula (III) are each independently substituted with hydrogen, halogen, a cyano group, a nitro group or an optionally substituted alkyl, alkenyl, alkynl, aralkyl, aryl or heteroaryl group or an optionally substituted alkylthio group or any substituted carbamoyl group, which also may be linked bridgingly to a moiety of formula (I), or a trifluoromethyl group or a trifluoromethoxy group or a moiety Racryl' of formula (IV),R1' is hydrogen or a (C1-C6)-alkyl group,X' is a carboxamide (-C(O)N-) or a carboxylic ester (-C(O)O-) or a sulphonamide (-SO2N-) group,Y' is a saturated or unsaturated or linear or branched optionally substituted moiety having 2-10 carbon atoms or a polyether having from one to five (-CH2-CH2-O-)- or (-C(CH3)H-CH2-O-)- groups or a polyamine having from one to five nitrogen atoms, andZ is oxygen or sulphur,c) the remaining carbon atoms of the compound of formula (I) are each independently substituted with hydrogen, halogen, a cyano group, a nitro group or an optionally substituted alkyl, alkenyl, alkynyl, aralkyl, aryl or heteroaryl group or an optionally substituted alkylthio group or a trifluoromethyl group or a trifluoromethoxy group. - Compound according to Claim 1, characterized in that it is substituted with the moiety of formula (III) on the carbon atom in position 5 of formula (I), wherein the moiety of formula (III) is preferably bonded to the carbon atom in position 5 via the carbon atom in position 8'.
- Compound according to either of Claims 1 and 2, characterized in that it is substituted with the moiety R of formula (II) on the carbon atom in position 6 of formula (I).
- Compound according to any of Claims 1 to 3, characterized in that the moiety of formula (III) is substituted with the moiety Racryl' of formula (IV) on the carbon atom in position 7'.
- Compound according to any of Claims 1 to 4, characterized in that X is carboxamide in moiety Racryl and/or X' is carboxamide in moiety Racryl'.
- Compound according to any of Claims 1 to 5, characterized in that R1 is hydrogen or a CH3 moiety in moiety Racryl and/or R1' is hydrogen or a CH3 moiety in moiety Racryl'.
- Compound according to any of Claims 1 to 6, characterized in that Y is a -CH2-CH2 group in moiety Racryl and/or Y1 is a -CH2-CH2 group in moiety Racryl'.
- Compound according to any of Claims 1 to 7, characterized in that Z is oxygen in moiety Racryl and/or Z' is oxygen in moiety Racryl'.
- Photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, wherein the writing monomers comprise a compound according to any of Claims 1 to 8.
- Holographic medium comprising matrix polymers, writing monomers and photoinitiators, wherein the writing monomers comprise a compound according to any of Claims 1 to 8.
- Holographic medium according to Claim 10, characterized in that the matrix polymers are crosslinked matrix polymers, preferably three-dimensionally crosslinked matrix polymers and most preferably are three-dimensionally crosslinked polyurethanes.
- Holographic medium according to either of Claims 10 and 11, characterized in that it comprises at least a fluorourethane as additive.
- Holographic medium according to any of Claims 10 to 12, characterized in that it is a film, preferably with a film thickness of 0.5 µm to 200 µm, more preferably with a film thickness of 0.8 µm to 50 µm and yet more preferably with a film thickness of 1 µm to 25 µm.
- Holographic medium according to any of Claims 10 to 13, characterized in that it contains at least one exposed hologram.
- Display comprising a holographic medium according to any of Claims 10 to 14.
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-
2015
- 2015-12-09 WO PCT/EP2015/079152 patent/WO2016091965A1/en active Application Filing
- 2015-12-09 KR KR1020177015767A patent/KR102583200B1/en active IP Right Grant
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CN107001246B (en) | 2021-02-02 |
KR20170094201A (en) | 2017-08-17 |
WO2016091965A1 (en) | 2016-06-16 |
TWI679189B (en) | 2019-12-11 |
EP3230261A1 (en) | 2017-10-18 |
TW201639812A (en) | 2016-11-16 |
JP6700280B2 (en) | 2020-05-27 |
US20170363957A1 (en) | 2017-12-21 |
US10241402B2 (en) | 2019-03-26 |
CN107001246A (en) | 2017-08-01 |
JP2018501224A (en) | 2018-01-18 |
KR102583200B1 (en) | 2023-09-27 |
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